Fluorine-containing polymer, resist composition prepared from same and novel fluorine-containing monomer

ABSTRACT

A fluorine-containing unsaturated cyclic compound represented by the formula (1)(a): 
                         
wherein Z 3  are the same or different and each is —Rf 3 -Z 4 , in which Z 4  is at least one functional group selected from the group consisting of OH group, COOH group, a derivative of carboxylic acid group and a functional group protected by a protective group which can convert the functional group to OH group by reaction with an acid; Rf 3  is a fluorine-containing alkylene group which has 1 to 30 carbon atoms and may have ether bond; n 11  is an integer of from 1 to 4.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of U.S. application Ser. No. 10/815,801filed Apr. 2, 2004 now U.S. Pat. No. 7,115,690, which is acontinuation-in-part of PCT international application No. PCT/JP02/10242filed on Oct. 2, 2002; the above-noted applications incorporated hereinby reference in their entirety.

BACKGROUND OF THE INVENTION

The present invention relates to a novel fluorine-containing unsaturatedcyclic compound, a novel fluorine-containing polymer having an aliphaticmonocyclic structure in its trunk chain, and a chemically amplifyingphotoresist composition which is obtained from the fluorine-containingpolymer, is excellent in transparency and possesses improved dry etchingresistance.

As a result of an increasing necessity for high integration of a largescale integrated circuit (LSI), microfabrication technology is requiredfor photolithography. In order to satisfy such requirements, there havebeen tried to use, as exposure light sources, a deep ultraviolet, a KrFexcimer laser beam (wavelength: 248 nm) and a ArF excimer laser beam(wavelength: 193 nm) which have a wavelength shorter than conventionalg-rays (wavelength: 436 nm) and i-rays (wavelength: 365 nm). Those lightsources are put into practical use.

Recently a process using a F₂ laser beam (wavelength: 157 nm) having awavelength in a vacuum ultraviolet region has been studied in anultra-microfabrication technology and is considered promising as anexposure technology aiming at a technology node of 0.1 μm.

On the other hand, in the pattern formation, a chemically amplifyingresist which becomes advantageous in transparency, resolution,sensitivity and dry etching resistance in cases of energy rays havingvarious wavelengths has been studied. The chemically amplifying resistmeans, for example, in case of a positive resist, an energy-sensitivecomposition comprising a resin being soluble in an alkali developingsolution and having an introduced substituent which has an effect ofinhibiting dissolution of the resin but is deprotected due to action ofan acid, and a compound which generates an acid by irradiation of energyrays such as light and electron beam (hereinafter referred to as aphotoacid generator). When the composition is irradiated with light orelectron beam, an acid is generated from the photoacid generator, and byheating (post-exposure bake, which may be hereinafter referred to as“PEB”) after the exposure to light, the substituent which has beengiving a dissolution inhibiting effect on the resin is deprotected dueto action of an acid. As a result, the exposed portion becomes solublein alkali, and by treating the exposed portion with an alkali developingsolution, a positive resist pattern can be obtained. In that case, theacid acts as a catalyst and exhibits its effect in a very small amount.Also action of the acid becomes active by the PEB and a chemicalreaction is accelerated like a chain reaction, and thus sensitivity isenhanced.

Examples of conventional resins for chemically amplifying resist arephenol resins in which a part or the whole of hydroxyl is protected by aprotective group such as acetal or ketal (KrF resist), methacrylic acidresins in which an acid-labile ester group is introduced to carboxyl(ArF resist) and the like.

However those conventional resist polymers have strong absorption in awavelength range of a vacuum ultraviolet region and have a significantproblem that transparency against F₂ laser beam having a wavelength of157 nm which is studied in a process for ultra fine pattern is low (anabsorption coefficient is high). Therefore for exposing with F₂ laser,it is necessary to make a resist film thickness very thin and it issubstantially difficult to use the polymers as a single layer F₂ resist.

R. R. Kunz, T. M. Bloomstein, et al. suggest in Journal of PhotopolymerScience and Technology (Vol. 12, No. 4 (1999) 561-569) thatfluorocarbons have good transparency at 157 nm as compared with othervarious materials and have possibility of use as a F₂ resist.

However in that literature, there is only description that existingfluorocarbon polymers are high in transparency at 157 nm, but there isno description as to preferable structure of fluorine-containingpolymers. Also, for example, with respect to a fluorine-containingpolymer having functional group necessary for a positive type ornegative type chemically amplifying resist, neither evaluation oftransparency nor synthesis of the polymer was made. Moreover theliterature does not suggest a fluorine-containing base polymer materialbeing preferable as a chemically amplifying resist and a preferableresist composition obtained therefrom at all, and there is found nopossibility of forming a F₂ resist pattern by using afluorine-containing polymer.

Thereafter A. E. Feiring, et al. of E.I. du Pont de Nemours and Companydisclosed in WO00/17712 pamphlet (published Mar. 30, 2000) that aspecific fluorine-containing polymer is useful for F₂ resistapplication.

That pamphlet describes the use of a fluorine-containing polymer havinga structural unit of fluoroolefin and a structural unit having apolycyclic condensed structure which is mainly a structural unit derivedfrom norbornene.

Also an acid-labile (acid-decomposable) functional group necessary for apositive type resist is introduced to the fluorine-containing polymer bycopolymerizing a conventional acrylic, methacrylic, norbornene or vinylester monomer with a monomer having an introduced acid-labile(acid-decomposable) functional group.

Further thereafter A. E. Feiring, et al. of E.I. du Pont de Nemours andCompany disclosed in WO00/67072 pamphlet (published Nov. 9, 2000) that afluorine-containing polymer having —C(Rf)(Rf′)OH or —C(Rf)(Rf′)O—Rb isuseful for F₂ resist application.

In that pamphlet, a structural unit of norbornene in which —C(Rf)(Rf′)OHor —C(Rf)(Rf′)O—Rb is bonded through a part of —CH₂OCH₂— is disclosed.Further there is disclosed norbornene derivatives having —C(Rf)(Rf′)OHor —C(Rf)(Rf′)O—Rb as an example of a fluorine-containing polymer to beused for a resist.

However in those patent publications, there is no description as to theuse of a fluorine-containing copolymer comprising a structural unit offluoroolefin and a structural unit having an aliphatic monocyclicstructure in its trunk chain, and further there is no description as toan aliphatic monocyclic structure to which a functional group necessaryfor a resist is introduced.

Further Katsuyama, et al. of Matsushita Electric Industrial Co., Ltd.proposed a method of forming a pattern with exposure light having awavelength of from 1 to 180 nm using a resist material containinghalogen atom, etc. (JP2000-321774A published Nov. 24, 2000). Howeverthere is disclosed only a methacrylic resin having a structural unit ofmethacrylic acid ester having —CH₂CF₃ group and —CH(CF₃)₂ group in itsside chain as a base resin having halogen atom for a resist, and neithera resin containing fluorine atom in its trunk chain nor a polymer havingan aliphatic monocyclic structure in its trunk chain is disclosed. Alsothere is disclosed no polymer which has, in an aliphatic monocyclicstructure, a functional group and is capable of working as a chemicallyamplifying resist (positive type or negative type).

There is generally known that dry etching resistance of a polymer isenhanced by introducing a norbornene backbone to the polymer. Howevertransparency, particularly transparency in a vacuum ultraviolet regionof conventional norbornene derivatives cannot be said to be sufficient.

The present inventors have found that fluoroolefins represented bytetrafluoroethylene have good copolymerizability with unsaturatedcompounds (monomers) of aliphatic monocyclic structure, and a novelfluorine-containing polymer was obtained. It has been considered thatdry etching resistance of monocyclic compounds was insufficient ascompared with compounds having polycyclic condensed structure. Howeverthe present inventors have found that the copolymer which is obtained inthe present invention and comprises fluoroolefin and an unsaturatedcompound (monomer) of aliphatic monocyclic structure has dry etchingresistance higher than that of an unsaturated compound having polycycliccondensed structure, for example, norbornene.

Also it was found that transparency in a vacuum ultraviolet region isexcellent as compared with the use of norbornene.

Also studies have been made as to introduction of an acid-reactivefunctional group necessary for a resist, and as a result, it was foundthat in addition to the fluoroolefin and unsaturated compound (monomer)of aliphatic monocyclic structure, a specific ethylenic monomer havingan acid-reactive functional group has good copolymerizability, whichmade it possible to introduce an acid-reactive functional group to apolymer. Further the present inventors have found a fluorine-containingpolymer in which an acid-reactive functional group is introduceddirectly to a monocyclic structure and also a novel unsaturated compoundof monocyclic structure having an acid-reactive functional group andpartly having fluorine atoms. The copolymer comprising such a novelunsaturated compound of monocyclic structure and a fluoroolefin exhibitsexcellent dry etching resistance and high transparency when used for aresist.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide a novelfluorine-containing polymer having an aliphatic monocyclic structure inits trunk chain.

The second object of the present invention is to provide a novelfluorine-containing unsaturated aliphatic monocyclic compound havingfunctional group.

The third object of the present invention is to provide a chemicallyamplifying photoresist composition which comprises a fluorine-containingaliphatic monocyclic polymer having an acid-reactive group and aphotoacid generator and can be used for a patterning process using F₂laser as light source.

The present inventors have made intensive studies to achieve theabove-mentioned objects and as a result, have found a novelfluorine-containing unsaturated aliphatic monocyclic compound and anovel fluorine-containing polymer having an aliphatic monocyclicstructure in its trunk chain and have found that the fluorine-containingpolymer is useful as a polymer for a resist.

Namely, the present inventors have made various studies with respect tocopolymerization of a fluoroolefin, typically tetrafluoroethylene withunsaturated monocyclic hydrocarbon compounds and as a result, have foundthat a specific unsaturated monocyclic hydrocarbon compound which canconstitute a ring in its trunk chain has good copolymerizability withfluoroolefins having 2 or 3 carbon atoms, and have found a novelfluorine-containing polymer.

The first of the present invention relates to novel fluorine-containingpolymers. The first novel fluorine-containing polymer is afluorine-containing polymer having an aliphatic monocyclic structure inthe polymer trunk chain which has a number average molecular weight offrom 500 to 1,000,000 and is represented by the formula (Ma):-(M1)-(M2a)-(N)-  (Ma)in whichthe structural unit M1 is a structural unit derived from an ethylenicmonomer having 2 or 3 carbon atoms and at least one fluorine atom, thestructural unit M2a is at least one structural unit which introduces analiphatic monocyclic structure in the polymer trunk chain and isrepresented by the formula (a):

wherein R¹ is at least one hydrocarbon group selected from the groupconsisting of a divalent hydrocarbon group which has 1 to 8 carbon atomsand constitutes a ring (which may be further substituted with ahydrocarbon group or a fluorine-containing alkyl group) and a divalenthydrocarbon group having ether bond which has the sum of carbon atomsand oxygen atoms of 2 to 8 and constitutes a ring (which may be furthersubstituted with a hydrocarbon group or a fluorine-containing alkylgroup); R² is an alkylene group which has 1 to 3 carbon atoms andconstitutes a ring; R³ and R⁴ are the same or different and each is adivalent alkylene group having 1 or 2 carbon atoms; n1, n2 and n3 arethe same or different and each is 0 or 1,the structural unit N is a structural unit derived from a monomercopolymerizable with the monomers to introduce the structural units M1and M2a, andthe structural units M1, M2a and N are contained in amounts of from 1 to99% by mole, from 1 to 99% by mole and from 0 to 98% by mole,respectively.

The second fluorine-containing polymer of the first invention is afluorine-containing polymer having an aliphatic monocyclic structure inthe polymer trunk chain which has a number average molecular weight offrom 500 to 1,000,000 and is represented by the formula (Mb):-(M1)-(M2b)-(N)-  (Mb)in whichthe structural units M1 and N are as defined in the above-mentionedformula (Ma),the structural unit M2b is at least one structural unit which introducesan aliphatic monocyclic structure in the trunk chain and is representedby the formula (b):

wherein R¹, R², R³, R⁴, n1, n2 and n3 are as defined in theabove-mentioned formula (a); Z are the same or different and each is:

R⁵

_(n5)Z¹wherein Z¹ is at least one functional group selected from the groupconsisting of OH group, COOH group, a derivative of carboxylic acidgroup and a functional group protected by a protective group which canconvert the functional group to OH group by reaction with an acid; R⁵ isa divalent organic group; n5 is 0 or 1; n4 is an integer of from 1 to 3,and the structural units M1, M2b and N are contained in amounts of from1 to 99% by mole, from 1 to 99% by mole and from 0 to 98% by mole,respectively.

The second of the present invention relates to a fluorine-containingunsaturated cyclic compound represented by the formula (1):

wherein Z³ are the same or different and each is —Rf³-Z⁴, in which Z⁴ isat least one functional group selected from the group consisting of OHgroup, COOH group, a derivative of carboxylic acid group and afunctional group protected by a protective group which can converted thefunctional group to OH group by reaction with an acid; Rf³ is afluorine-containing alkylene group which has 1 to 30 carbon atoms andmay have ether bond; n11 is an integer of from 1 to 4.

The third of the present invention relates to a photoresist compositionwhich comprises:

-   (A-1) a fluorine-containing polymer having OH group, COOH group    and/or a group which can be dissociated by an acid and converted to    OH group or COOH group,-   (B) a photoacid generator and-   (C) a solvent,    in which the fluorine-containing polymer (A-1) is a polymer    comprising a structural unit derived from a fluoroolefin and a    structural unit derived from a monomer introducing an aliphatic    monocyclic structure in the polymer trunk chain.

The fourth of the present invention relates to a photoresist compositionwhich comprises:

-   (A-2) a fluorine-containing polymer having OH group which has    recurring units of an aliphatic monocyclic structure in the polymer    trunk chain, in which OH group or a moiety having OH group is bonded    to the carbon atom constituting the aliphatic monocyclic structure,-   (B) a photoacid generator and-   (C) a solvent,    in which when in the recurring units of the aliphatic monocyclic    structure of the fluorine-containing polymer (A-2), the carbon atom    bonded to OH group is named the first carbon atom and a structure    consisting of the first carbon atom up to the neighboring fourth    carbon atom is assumed to be a model structure, the model structure    having OH group satisfies Equation 1:    ΔH=H(M-O⁻)+200−H(M-OH)≦75  (Equation 1)    and further Equation 2:    ΔH=H(M-O⁻)+200−H(M-OH)≦70  (Equation 2)    wherein H(M-OH) is a produced enthalpy of the model structure,    H(M-O⁻) is a produced enthalpy of the model structure after    dissociation of the OH group and a produced enthalpy of hydrogen ion    is assumed to be a constant of 200 kJ/mol.

The fifth of the present invention relates to a photoresist compositionwhich comprises:

-   (A-3) a fluorine-containing polymer having OH group which has    recurring units of an aliphatic monocyclic structure in the polymer    trunk chain, in which OH group or a moiety having OH group is bonded    to the carbon atom constituting the aliphatic monocyclic structure,-   (B) a photoacid generator and-   (C) a solvent,    in which the recurring units of the aliphatic monocyclic structure    of the fluorine-containing polymer (A-3) have a structure    represented by the formula (50):

wherein Rf¹¹ is a perfluoroalkyl group having 1 to 20 carbon atoms; Z¹⁰is fluorine atom or a perfluoroalkyl group having 1 to 20 carbon atoms.

The OH group in the recurring units of the aliphatic monocyclicstructure may be protected by a protective group.

The sixth of the present invention relates to a photoresist compositionwhich comprises:

-   (A-5) a fluorine-containing polymer having OH group which has    recurring units of an aliphatic monocyclic structure in the polymer    trunk chain, in which OH group or a moiety having OH group is bonded    to the carbon atom constituting the aliphatic monocyclic structure,-   (B) a photoacid generator and-   (C) a solvent,    in which the fluorine-containing polymer (A-5) is a polymer having a    structural unit represented by the formula (53):

wherein Rf⁵⁰ and Rf⁵¹ are the same or different and each is aperfluoroalkyl group having 1 to 20 carbon atoms; X¹⁰ and X¹¹ are thesame or different and each is H, F, an alkyl group having 1 to 20 carbonatoms or a fluorine-containing alkyl group which has 1 to 20 carbonatoms and may have ether bond; X¹² is hydrogen atom, fluorine atom, analkyl group having 1 to 20 carbon atoms, a fluorine-containing alkylgroup which has 1 to 20 carbon atoms and may have ether bond, OH groupor a group represented by the formula:

wherein Rf⁵² and Rf⁵³ are the same or different and each is aperfluoroalkyl group having 1 to 20 carbon atoms; R⁵⁰ is at least oneselected from an alkylene group or fluorine-containing alkylene groupwhich has 1 to 3 carbon atoms and constitutes a ring; R⁵¹ and R⁵² arethe same or different and each is at least one selected from a divalenthydrocarbon group which has 1 to 7 carbon atoms and constitutes a ring,oxygen atom, a divalent hydrocarbon group having ether bond which hasthe sum of oxygen atoms and carbon atoms of 2 to 7 and constitutes aring, a divalent fluorine-containing alkylene group which has 1 to 7carbon atoms and constitutes a ring or a divalent fluorine-containingalkylene group having ether bond which has the sum of oxygen atoms andcarbon atoms of 2 to 7 and constitutes a ring; the sum of carbon atomsconstituting a trunk chain in R⁵¹ and R⁵² is not more than 7, and OHgroup or a group represented by the formula:

wherein Rf⁵² and Rf⁵³ are as defined above, may be bonded to any ofcarbon atoms in R⁵¹; R⁵³ and R⁵⁴ are the same or different and each is adivalent alkylene group having 1 or 2 carbon atoms or a divalentfluorine-containing alkylene group having 1 or 2 carbon atoms; n50, n51,n52, n53 and n54 are the same or different and each is 0 or 1.

The seventh of the present invention relates to a photoresistcomposition which comprises:

-   (A-5) a fluorine-containing polymer having OH group which has    recurring units of an aliphatic monocyclic structure in the polymer    trunk chain, in which OH group or a moiety having OH group is bonded    to the carbon atom constituting the aliphatic monocyclic structure,-   (B) a photoacid generator and-   (C) a solvent,    in which the fluorine-containing polymer (A-5) is a polymer having a    structural unit represented by the formula (54):

wherein Rf⁵⁰ is a perfluoroalkyl group having 1 to 20 carbon atoms; X¹⁰and X¹¹ are the same or different and each is H, F, an alkyl grouphaving 1 to 20 carbon atoms or a fluorine-containing alkyl group whichhas 1 to 20 carbon atoms and may have ether bond; R⁵⁰ is at least oneselected from an alkylene group or fluorine-containing alkylene groupwhich has 1 to 3 carbon atoms and constitutes a ring; R⁵¹ and R⁵² arethe same or different and each is at least one selected from a divalenthydrocarbon group which has 1 to 7 carbon atoms and constitutes a ring,oxygen atom, a divalent hydrocarbon group having ether bond which hasthe sum of oxygen atoms and carbon atoms of 2 to 7 and constitutes aring, a divalent fluorine-containing alkylene group which has 1 to 7carbon atoms and constitutes a ring or a divalent fluorine-containingalkylene group having ether bond which has the sum of oxygen atoms andcarbon atoms of 2 to 7 and constitutes a ring; the sum of carbon atomsconstituting a trunk chain in R⁵¹ and R⁵² is not more than 7, and OHgroup or a group represented by the formula:

wherein Rf⁵² and Rf⁵³ are the same or different and each is aperfluoroalkyl group having 1 to 20 carbon atoms, may be bonded to anyof carbon atoms in R⁵¹; R⁵³ and R⁵⁴ are the same or different and eachis a divalent alkylene group having 1 or 2 carbon atoms or a divalentfluorine-containing alkylene group having 1 or 2 carbon atoms; n50, n51,n52, n53 and n54 are the same or different and each is 0 or 1.

It is preferable that in the formula (53), X¹² is fluorine atom or aperfluoroalkyl group having 1 to 20 carbon atoms and that in R⁵¹ or R⁵²of the formula (54), at least one fluorine atom or perfluoroalkyl grouphaving 1 to 20 carbon atoms is bonded to at least one of neighboringcarbon atoms of the carbon atom bonded to the OH group.

Further in the formula (54), also preferred is a structural unit having,in the structure of R⁵¹, at least one structural unit represented by theformula:

wherein Rf⁵² is as defined above.

The eighth of the present invention relates to a fluorine-containingpolymer having a number average molecular weight of from 500 to1,000,000 which is represented by the formula (61):-(M3-1)-(N-3-1)-  (61)in which M3-1 is a structural unit represented by the formula (53):

wherein Rf⁵⁰ and Rf⁵¹ are the same or different and each is aperfluoroalkyl group having 1 to 20 carbon atoms; X¹⁰ and X¹¹ are thesame or different and each is H, F, an alkyl group having 1 to 20 carbonatoms or a fluorine-containing alkyl group which has 1 to 20 carbonatoms and may have ether bond; X¹² is hydrogen atom, fluorine atom, analkyl group having 1 to 20 carbon atoms, a fluorine-containing alkylgroup which has 1 to 20 carbon atoms and may have ether bond, OH groupor a group represented by the formula:

wherein Rf⁵² and Rf⁵³ are the same or different and each is aperfluoroalkyl group having 1 to 20 carbon atoms; R⁵⁰ is at least oneselected from an alkylene group or fluorine-containing alkylene groupwhich has 1 to 3 carbon atoms and constitutes a ring; R⁵¹ and R⁵² arethe same or different and each is at least one selected from a divalenthydrocarbon group which has 1 to 7 carbon atoms and constitutes a ring,oxygen atom, a divalent hydrocarbon group having ether bond which hasthe sum of oxygen atoms and carbon atoms of 2 to 7 and constitutes aring, a divalent fluorine-containing alkylene group which has 1 to 7carbon atoms and constitutes a ring or a divalent fluorine-containingalkylene group having ether bond which has the sum of oxygen atoms andcarbon atoms of 2 to 7 and constitutes a ring; the sum of carbon atomsconstituting a trunk chain in R⁵¹ and R⁵² is not more than 7, and OHgroup or a group represented by the formula:

wherein Rf⁵² and Rf⁵³ are as defined above, may be bonded to any ofcarbon atoms in R⁵¹; R⁵³ and R⁵⁴ are the same or different and each is adivalent alkylene group having 1 or 2 carbon atoms or a divalentfluorine-containing alkylene group having 1 or 2 carbon atoms; n50, n51,n52, n53 and n54 are the same or different and each is 0 or 1,N3-1 is a structural unit derived from a monomer copolymerizable withthe monomer to introduce the structural unit M3-1, andthe structural units M3-1 and N3-1 are contained in amounts of from 0.1to 100% by mole and from 0 to 99.9% by mole, respectively.

The ninth of the present invention relates to a fluorine-containingpolymer having a number average molecular weight of from 500 to1,000,000 which is represented by the formula (61):-(M3-1)-(N-3-1)-  (61)in which M3-1 is a structural unit represented by the formula (54):

wherein Rf⁵⁰ is a perfluoroalkyl group having 1 to 20 carbon atoms; X¹⁰and X¹¹ are the same or different and each is H, F, an alkyl grouphaving 1 to 20 carbon atoms or a fluorine-containing alkyl group whichhas 1 to 20 carbon atoms and may have ether bond; R⁵⁰ is at least oneselected from an alkylene group or fluorine-containing alkylene groupwhich has 1 to 3 carbon atoms and constitutes a ring; R⁵¹ and R⁵² arethe same or different and each is at least one selected from a divalenthydrocarbon group which has 1 to 7 carbon atoms and constitutes a ring,oxygen atom, a divalent hydrocarbon group having ether bond which hasthe sum of oxygen atoms and carbon atoms of 2 to 7 and constitutes aring, a divalent fluorine-containing alkylene group which has 1 to 7carbon atoms and constitutes a ring or a divalent fluorine-containingalkylene group having ether bond which has the sum of oxygen atoms andcarbon atoms of 2 to 7 and constitutes a ring; the sum of carbon atomsconstituting a trunk chain in R⁵¹ and R⁵² is not more than 7, and OHgroup or a group represented by the formula:

wherein Rf⁵² and Rf⁵³ are the same or different and each is aperfluoroalkyl group having 1 to 20 carbon atoms, may be bonded to anyof carbon atoms in R⁵¹; R⁵³ and R⁵⁴ are the same or different and eachis a divalent alkylene group having 1 or 2 carbon atoms or a divalentfluorine-containing alkylene group having 1 or 2 carbon atoms; n50, n51,n52, n53 and n54 are the same or different and each is 0 or 1,N3-1 is a structural unit derived from a monomer copolymerizable withthe monomer to introduce the structural unit M3-1, andthe structural units M3-1 and N3-1 are contained in amounts of from 0.1to 100% by mole and from 0 to 99.9% by mole, respectively.

It is preferable that in the formula (53), X¹² is fluorine atom or aperfluoroalkyl group having 1 to 20 carbon atoms, or that in R⁵¹ or R⁵²of the formula (54), at least one of fluorine atom or a perfluoroalkylgroup having 1 to 20 carbon atoms is bonded to at least one ofneighboring carbon atoms of the carbon atom bonded to OH group.

Further in the formula (54), also preferred is a structural unit having,in the structure of R⁵¹, at least one structural unit represented by theformula:

wherein Rf⁵² is as defined above.

Further it is preferable that the above-mentioned structural unit M3-1is a structural unit satisfying the above-mentioned Equation 1 andfurther Equation 2.

The tenth of the present invention relates to a fluorine-containingcyclopentene having OH group which is represented by the formula (70):

wherein Rf⁷⁰ is a perfluoroalkyl group having 1 to 20 carbon atoms; X⁷⁰is fluorine atom or a perfluoroalkyl group having 1 to 20 carbon atoms;X⁷¹ is hydrogen atom, fluorine atom, a hydrocarbon group having 1 to 20carbon atoms or a perfluoroalkyl group having 1 to 20 carbon atoms; X⁷²is hydrogen atom, fluorine atom, OH group, a hydrocarbon group having 1to 20 carbon atoms or a perfluoroalkyl group having 1 to 20 carbonatoms; X⁷³ is hydrogen atom, fluorine atom, a hydrocarbon group having 1to 20 carbon atoms or a perfluoroalkyl group having 1 to 20 carbonatoms; when X⁷² is OH group, X⁷³ is not fluorine atom.

In the above-mentioned formula (70), it is preferable that both of X⁷⁰and X⁷¹ are fluorine atoms or perfluoroalkyl groups having 1 to 20carbon atoms or X⁷² is OH group and X⁷³ is a perfluoroalkyl group having1 to 20 carbon atoms.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph in which ΔH and pKa calculated in Experimental Example1 are plotted.

DETAILED DESCRIPTION

First, the first novel fluorine-containing polymer of the presentinvention is explained below.

The first novel fluorine-containing polymer is, as mentioned above, afluorine-containing polymer having an aliphatic monocyclic structure inthe polymer trunk chain which has a number average molecular weight offrom 500 to 1,000,000 and is represented by the formula (Ma):-(M1)-(M2a)-(N)-  (Ma)in whichthe structural unit M1 is a structural unit derived from an ethylenicmonomer having 2 or 3 carbon atoms and at least one fluorine atom, thestructural unit M2a is at least one structural unit which introduces analiphatic monocyclic structure in the polymer trunk chain and isrepresented by the formula (a):

wherein R¹ is at least one hydrocarbon group selected from the groupconsisting of a divalent hydrocarbon group which has 1 to 8 carbon atomsand constitutes a ring (which may be further substituted with ahydrocarbon group or a fluorine-containing alkyl group) and a divalenthydrocarbon group having ether bond which has the sum of carbon atomsand oxygen atoms of 2 to 8 and constitutes a ring (which may be furthersubstituted with a hydrocarbon group or a fluorine-containing alkylgroup); R² is an alkylene group which has 1 to 3 carbon atoms andconstitutes a ring; R³ and R⁴ are the same or different and each is adivalent alkylene group having 1 or 2 carbon atoms; n1, n2 and n3 arethe same or different and each is 0 or 1,the structural unit N is a structural unit derived from a monomercopolymerizable with the monomers to introduce the structural units M1and M2a, andthe structural units M1, M2a and N are contained in amounts of from 1 to99% by mole, from 1 to 99% by mole and from 0 to 98% by mole,respectively.

In the structural unit M2a introducing the monocyclic structure, thedivalent hydrocarbon groups R¹ and R² constitute a ring, and twoneighboring carbon atoms of the divalent hydrocarbon group R¹ may bebonded to each other without R².

The divalent hydrocarbon group R¹ in the structural unit M2a is adivalent hydrocarbon group which constitutes a ring and has 1 to 8carbon atoms, and hydrogen atom thereof may be substituted with ahydrocarbon group (for example, a hydrocarbon group having 1 to 20carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms) or afluorine-containing alkyl group (for example, a fluorine-containingalkyl group which has 1 to 20 carbon atoms and may have ether bond,preferably a fluorine-containing alkyl group which has 1 to 5 carbonatoms and may have ether bond or a perfluoroalkyl group which may haveether bond). R¹ may have an unsaturated bond.

The divalent hydrocarbon group R¹ may have ether bond, and in that case,is a group which has the sum of carbon atoms and oxygen atoms of from 2to 8 and constitutes a ring. Hydrogen atoms of R¹ also may besubstituted with hydrocarbon groups or fluorine-containing alkyl groupssimilar to those mentioned above, and R¹ may have an unsaturated bond.

In the first fluorine-containing polymer of the present invention, thestructural unit M2a constituting a ring does not have functional group.

Examples of preferred structural unit M2a are structural units derivedfrom unsaturated aliphatic monocyclic compounds such as:

The structural unit M2a encompasses those in which hydrogen atoms otherthan the hydrogen atoms bonded to the carbon atoms of carbon-carbondouble bond are substituted with a hydrocarbon group (for example, ahydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl grouphaving 1 to 5 carbon atoms) or a fluorine-containing alkyl group (forexample, a fluorine-containing alkyl group which has 1 to 20 carbonatoms and may have ether bond, preferably a fluorine-containing alkylgroup which has 1 to 5 carbon atoms and may have ether bond or aperfluoroalkyl group which may have ether bond).

Among them, preferred are unsaturated compounds constituting athree-membered ring (in the formula (a), any of n1, n2 and n3 are 0 andthe number of carbon atoms of R¹ constituting a ring is 1),five-membered ring (in the formula (a), any of n1, n2 and n3 are 0 andthe number of carbon atoms of R¹ constituting a ring is 3) oreight-membered ring (in the formula (a), any of n1, n2 and n3 are 0 andthe number of carbon atoms of R¹ constituting a ring is 6) from theviewpoint of good copolymerizability with fluoroolefins, andparticularly preferred are three-membered ring and eight-membered ring.

More concretely it is preferable that the structural unit M2a is astructural unit represented by the formula (a-1):

wherein R⁶ is selected from hydrogen atom, an alkyl group having 1 to 5carbon atoms or a fluorine-containing alkyl group which has 1 to 5carbon atoms and may have ether bond; n6 is 0 or an integer of from 1 to12, orthe formula (a-2):

wherein R⁷ and R⁸ are the same or different and each is hydrogen atom,an alkyl group having 1 to 5 carbon atoms or a fluorine-containing alkylgroup which has 1 to 5 carbon atoms and may have ether bond.

The second novel fluorine-containing polymer of the present inventionis, as mentioned above, a fluorine-containing polymer having analiphatic monocyclic structure in the polymer trunk chain which has anumber average molecular weight of from 500 to 1,000,000 and isrepresented by the formula (Mb):-(M1)-(M2b)-(N)-  (Mb)in whichthe structural units M1 and N are as defined in the above-mentionedformula (Ma),the structural unit M2b is at least one structural unit which introducesan aliphatic monocyclic structure in the polymer trunk chain and isrepresented by the formula (b):

wherein R¹, R², R³, R⁴, n 1, n2 and n3 are as defined in theabove-mentioned formula (a); Z are the same or different and each is:

R⁵

_(n5)Z¹wherein Z¹ is at least one functional group selected from the groupconsisting of OH group, COOH group, a derivative of carboxylic acidgroup and a functional group protected by a protective group which canconvert the functional group to OH group by reaction with an acid; R⁵ isa divalent organic group; n5 is 0 or 1; n4 is an integer of from 1 to 3,and the structural units M1, M2b and N are contained in amounts of from1 to 99% by mole, from 1 to 99% by mole and from 0 to 98% by mole,respectively.

Those fluorine-containing polymers have a moiety Z having functionalgroup which is introduced to carbon atom constituting a ring structureequal to the ring structure of the above-mentioned structural unit M2ahaving a ring structure, and photosensitivity necessary for resistapplication and various useful functions for other applications can beimparted to the polymer.

Particularly in the resist application, it is preferable to introducethe functional group directly to the ring structure because a polymerhaving excellent dry etching resistance and transparency can beobtained.

The moiety Z having functional group is represented by the formula:

R⁵

_(n5)Z¹and the functional group Z¹ is at least one functional group selectedfrom the group consisting of OH group, COOH group, a derivative ofcarboxylic acid group and a functional group protected by a protectivegroup which can convert the functional group to OH group by reactionwith an acid.

Among them, the derivative of carboxylic acid group is selected fromcarboxylic acid esters, functional groups protected by a protectivegroup which can convert the functional group to COOH group due toreaction with an acid, carboxylic acid halides and acid amides.Preferred are carboxylic acid esters and functional groups protected bya protective group which can convert the functional group to COOH groupdue to reaction with an acid. The derivative of carboxylic acid group isselected, for example, from —COOR¹⁰, wherein R¹⁰ is an alkyl grouphaving 1 to 10 carbon atoms or —COO—P group mentioned infra.

The functional group (abbreviated to —COO—P) protecting theabove-mentioned functional group with a protective group (—P) which canconvert the functional group to COOH group due to reaction with an acidis a functional group necessary, for example, for the use in positivetype resist application, and has a function that the protective group(—P) is released due to reaction with an acid generated from a photoacidgenerator and converts the functional group to COOH group, therebymaking a polymer soluble in an alkali developing solution though thewhole polymer is insoluble in an alkali developing solution due toaction of the protective group before the reaction with an acid.

Examples of the functional group (—COO—P) having a protective groupwhich converts the functional group to COOH group due to reaction withan acid are:

and the like, wherein R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³⁶, R³⁷and R³⁸ are the same or different and each is a hydrocarbon group having1 to 10 carbon atoms; R³³ and R³⁴ are the same or different and each isH or a hydrocarbon group having 1 to 10 carbon atoms; R³⁵ is a divalenthydrocarbon group having 2 to 10 carbon atoms. More concretely there arepreferably:

and the like, wherein R³² is as defined above.

The functional group (abbreviated to —O—P) protecting theabove-mentioned functional group with a protective group (—P) which canconvert the functional group to —OH group due to reaction with an acidis a functional group necessary, for example, for the use in positivetype resist application, and has a function that the protective group(—P) is released due to reaction with an acid generated from a photoacidgenerator and converts the functional group to OH group, thereby makinga polymer soluble in an alkali developing solution though the wholepolymer is insoluble in an alkali developing solution due to action ofthe protective group before the reaction with an acid.

Examples of the functional group (—O—P) having a protective group whichconverts the functional group to —OH group due to reaction with an acidare preferably groups represented by:

wherein R²¹, R²², R²³ and R²⁴ are the same or different and each is analkyl group having 1 to 5 carbon atoms. More concretely there arepreferably:

and among them, from the viewpoint of good reactivity with an acid,preferred are:

and further from the viewpoint of good transparency, preferred are—OC(CH₃)₃, —OCH₂OCH₃ and —OCH₂OC₂H₅.

The moiety Z having functional group may have R⁵, or the moiety Z maynot have R⁵ and the functional group Z¹ may be bonded directly to thering structure.

When the moiety Z have R⁵, R⁵ may be one selected from divalent organicgroups. Examples thereof are preferably a divalent hydrocarbon groupwhich has 1 to 30 carbon atoms and may have ether bond and afluorine-containing divalent alkylene group having 1 to 30 carbon atomsand ether bond.

Examples of preferred moiety Z having functional group are thoserepresented by the formula:—(R⁹)_(n7)—COOR¹⁰,wherein R⁹ is an alkylene group which has 1 to 10 carbon atoms and mayhave ether bond or a fluorine-containing alkylene group which has 1 to10 carbon atoms and may have ether bond; R¹⁰ is hydrogen atom or analkyl group having 1 to 10 carbon atoms; n7 is 0 or 1. More concretelythere are:

-   —COOR¹⁰, —CH₂COOR¹⁰, —CH₂CH₂COOR¹⁰,-   —CH₂CH(CH₃)COOR¹⁰,-   —CF₂COOR¹⁰, —CF₂CF₂COOR¹⁰, —CH₂CH₂CF₂CF₂COOR¹⁰,-   —OCH₂COOR¹⁰    and the like.

Also Z is preferably an alcohol structure represented by the formula:

wherein R¹¹ is an alkylene group which has 1 to 5 carbon atoms and mayhave ether bond or a fluorine-containing alkylene group which has 1 to 5carbon atoms and may have ether bond; R¹² and R¹³ are the same ordifferent and each is hydrogen atom, an alkyl group having 1 to 10carbon atoms, an aryl group having 3 to 10 carbon atoms, afluorine-containing alkyl group which has 1 to 10 carbon atoms and mayhave ether bond or a fluorine-containing aryl group which has 3 to 10carbon atoms and may have ether bond; n8 is 0 or 1. Among them,preferred is a structure having fluorine atom, for example, a structurerepresented by the formula:

wherein Rf¹ is a fluorine-containing alkyl group which has 1 to 10carbon atoms and may have ether bond; Rf² is hydrogen atom, an alkylgroup having 1 to 10 carbon atoms, an aryl group having 3 to 10 carbonatoms or a fluorine-containing alkyl group which has 1 to 10 carbonatoms and may have ether bond; n9 is 0 or an integer of from 1 to 5; n10 is 0 or 1, from the viewpoint of transparency and solubility in adeveloping solution in the case of resist application.

In the above-mentioned fluorine-containing alcohol structure, it isfurther preferable that Rf¹ and Rf² are the same or different and eachis a perfluoroalkyl group having 1 to 5 carbon atoms, from the viewpointof transparency and solubility in a developing solution.

Examples of preferred alcohol structure are:

and the like.

In the second fluorine-containing polymer of the present invention,example of preferred structural unit M2b forming a ring is a structuralunit represented by the formula (b-1):

wherein Z and n4 are as defined in the formula (b), and examples of themoiety having functional group are the same as those preferablyexemplified supra.

Also the present inventors have found that when a specific diallylcompound having functional group is subjected to cyclic copolymerizationwith a fluoroolefin, a fluorine-containing copolymer having a monocyclicstructure in the polymer trunk chain can be obtained.

Thereby structural units represented by the formula (b-2):

and/or the formula (b-3):

wherein Z and n4 are as defined above, can be obtained.

Concretely when, for example, a diallyl compound represented by:

wherein Z⁵ is the same as the above-mentioned Z and Z⁶ is H or is thesame as the above-mentioned Z, is subjected to cyclic copolymerizationwith a fluoroolefin, structural units represented by the formula (b-4):

and/or the formula (b-5):

wherein Z⁵ and Z⁶ are as defined above, can be obtained.

In the above-mentioned formulae (b-4) and (b-5), it is preferable fromthe viewpoint of copolymerizability that Z⁵ and Z⁶ are the same ordifferent and each is at least one selected from COOH or a derivative ofcarboxylic acid group.

Example of preferred derivative of carboxylic acid group is one selectedfrom carboxylic acid esters, functional groups protected by a protectivegroup which can convert the functional group to COOH group due toreaction with an acid, acid halides and acid amides.

In the fluorine-containing polymer of the present invention, thestructural unit M1 derived from a fluoroolefin is at least onestructural unit selected from structural units derived fromfluorine-containing ethylenic monomers having 2 or 3 carbon atoms.Examples thereof are, for instance, tetrafluoroethylene,chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride,trifluoroethylene, hexafluoropropylene and the like.

Among them, preferred are structural units derived fromtetrafluoroethylene and chlorotrifluoroethylene because transparency anddry etching resistance can be improved in resist application.

In the polymers of the formulae (Ma) and (Mb) of the present invention,the structural unit M1, the structural unit M2a or M2b and thestructural unit N are contained in amounts of from 1 to 99% by mole,from 1 to 99% by mole and from 0 to 98% by mole, respectively. Providedthat (M1)+(M2a) or (M1)+(M2b) is 100% by mole, a percent by mole ratioof (M1)/(M2a) or (M1)/(M2b) is preferably 80/20 to 20/80, morepreferably 70/30 to 30/70, further preferably 60/40 to 40/60.

The present inventors have found that a specific ethylenic monomerhaving functional group can be copolymerized in addition to thefluoroolefin and the above-mentioned monomer being capable ofintroducing a monocyclic structure, thereby making it possible tointroduce the functional group to the fluorine-containing polymer havinga monocyclic structure in its trunk chain.

Accordingly photosensitivity necessary in resist application and varioususeful functions necessary in other applications can be imparted to thepolymer.

The structural unit derived from an ethylenic monomer having functionalgroup which is copolymerized with the fluoroolefin and the monomerintroducing the monocyclic structure is a structural unit derived froman ethylenic monomer and represented by the formula (N-1):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is a fluorine-containing alkylene group having 1 to 40 carbonatoms or a fluorine-containing alkylene group having 2 to 100 carbonatoms and ether bond; a is 0 or an integer of from 1 to 3; b and c arethe same or different and each is 0 or 1; Z² is at least one functionalgroup selected from the group consisting of OH group, COOH group, aderivative of carboxylic acid group and a functional group protected bya protective group which can convert the functional group to OH groupdue to reaction with an acid.

Examples thereof are, for instance, as follows.

(i) Structural unit derived from acrylic monomer and represented by:

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; R is selected from hydrogen atom, a hydrocarbon grouphaving 1 to 20 carbon atoms, a fluorine-containing alkyl group having 1to 20 carbon atoms, a fluorine-containing alkyl group having 2 to 100carbon atoms and ether bond or a fluorine-containing aryl group having 3to 20 carbon atoms.

In the above-mentioned formula, examples of preferred —R are:

-   hydrogen atom,-   —C(CH₃)₃, —CH₂CH₂OH, —(CH₂)_(m)(CF₂)_(n)—F, —(CH₂)_(m)(CF₂)_(n)—H,-   —(CH₂)_(m)(CF₂)_(n)—Cl, (m is an integer of from 1 to 5, n is an    integer of from 1 to 10)-   —CH(CF₃)₂, —CH₂CFHCF₃, —(CH₂)_(m)(CF₂)_(n)—CF(CF₃)₂, (m is an    integer of from 1 to 5, n is an integer of from 1 to 10)

(m is an integer of from 1 to 10)

and the like.

Examples thereof are, for instance, acrylic acid, methacrylic acid,α-fluoroacrylic acid, α-trifluoromethylacrylic acid, acrylic acidesters, α-fluoroacrylic acid esters, methacrylic acid esters,α-trifluoromethylacrylic acid esters, hydroxyethyl acrylate,hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate,acrylamides, methacrylamides and the like.

The introduction of the structural unit derived therefrom is preferredbecause it is possible to enhance solubility in a solvent,photosensitivity with a photoacid generator, adhesion to a substrate andcompatibility with a photoacid generator and other additives.

It is preferable that at least any one of X¹, X² and X³ has fluorineatom and/or X³ is a trifluoromethyl group, from the viewpoint oftransparency and dry etching resistance. It is particularly preferablethat X³ is fluorine atom or a trifluoromethyl group.

(ii) Structural unit derived from fluorine-containing ethylenic monomerhaving functional group and represented by:

wherein X¹, X², X³, X⁴, a, b, Rf and Z² are as defined in the formula(N-1).Particularly preferred is a structural unit represented by:

wherein Rf and Z² are as defined in the formula (N-1).

Concretely there are preferably structural units derived fromfluorine-containing ethylenic monomers such as:

and the like, wherein Z² is as defined in the formula (N-1). Alsopreferred is a structural unit represented by the formula:

wherein Rf and Z² are as defined in the formula (N-1). Concretely thereare preferably structural units derived from monomers such as:

and the like, wherein Z² is as defined in the formula (N-1).

Examples of the other fluorine-containing ethylenic monomer havingfunctional group are:

-   CF₂═CFCF₂—O—Rf-Z², CF₂═CF—Rf-Z²,-   CH₂═CH—Rf-Z², CH₂═CHO—Rf-Z²    and the like, wherein Rf and Z² are as defined in the formula (N-1).    More concretely there are:

and the like, wherein Z² is as defined in the formula (N-1).

Examples of the functional group Z² contained in the above-mentionedrespective structural units N1 are preferably the same as the examplesof the above-mentioned functional group Z¹.

The fluorine-containing polymer of the present invention having thestructural unit N1 having functional group is represented by the formula(Ma-1):-(M1)-(M2a)-(N1)-(N)-  (Ma-1)wherein M1 and M2a are as defined in the above-mentioned formula (Ma)and the structural unit N1 is the same as the formula (N-1). Examples ofpreferred structural units M1, M2a and N1 are the same as the preferredexamples mentioned supra.

Further the structural unit N1 having functional group may be introducedto a fluorine-containing polymer having functional group on the ring,namely, the polymer is represented by the formula (Mb-1):-(M1)-(M2b)-(N1)-(N)-  (Mb-1)wherein M1 and M2b are as defined in the formula (Mb) and the structuralunit N1 is the same as the formula (N-1). Examples of preferredstructural units M1, M2b and N1 are preferably the same as the preferredexamples mentioned supra. The polymer represented by the formula (Mb-1)is preferred because functional groups can be introduced in a highercontent and resolution can be improved in the case of use in resistapplication.

With respect to proportions of each structural unit in the polymers ofthe formulae (Ma-1) and (Mb-1) of the present invention, the structuralunits M1, M2a or M2b, N1 and N are contained in amounts of from 1 to 98%by mole, from 1 to 98% by mole, from 1 to 98% by mole and from 0 to 97%by mole, respectively. It is preferable that when (M1)+(M2a)+(N1) or(M1)+(M2b)+(N1) is 100% by mole, a percent by mole ratio of((M1)+(M2a))/(N1) or ((M1)+(M2b))/(N1) is 99/1 to 20/80, more preferably95/5 to 30/70, further preferably 90/10 to 40/60.

In the formulae (Ma), (Mb), (Ma-1) and (Mb-1) of the present invention,the structural unit N is an optional component copolymerizable with theother structural units.

Examples of the optional component are, for instance,

-   (i) Structural units derived from fluorine-containing ethylenic    monomers (Excluding M1)

For example, there are preferably structural units derived from monomerssuch as:

and the like, wherein X is selected from H, F and Cl, m is from 2 to 10.

-   (ii) Structural units derived from ethylenic monomers having no    fluorine

The structural units derived from ethylenic monomers having no fluorinemay be introduced to the polymer within a range not loweringtransparency and dry etching resistance (within a range where therefractive index does not increase).

The introduction of these structural units is preferred since adhesionto a substrate is improved, solubility in a general-purpose solvent isenhanced and compatibility with, for example, a photoacid generator andadditives to be added as case demands can be improved.

Examples of the non-fluorine-containing ethylenic monomer are asfollows.

α-Olefins:

Ethylene, propylene, butene, vinyl chloride, vinylidene chloride and thelike.

Vinyl Ether or Vinyl Ester Monomers:

CH₂═CHOR, CH₂═CHOCOR (R: hydrocarbon group having 1 to 20 carbon atoms)and the like.

Allyl Monomers:

CH₂═CHCH₂Cl, CH₂═CHCH₂OH, CH₂═CHCH₂COOH,

CH₂═CHCH₂Br and the like.

Allyl Ether Monomers:

CH₂═CHCH₂OR

(R: hydrocarbon group having 1 to 20 carbon atoms),

and the like.

The molecular weight of the fluorine-containing polymers of the formulae(Ma), (Mb), (Ma-1) and (Mb-1) of the present invention can be selectedin a range of from 500 to 1,000,000 in number average molecular weightdepending on application, purpose and form in use of the polymer.Preferred molecular weight is from 1,000 to 700,000, more preferablyfrom about 2,000 to about 500,000. When the molecular weight is too low,heat resistance and mechanical properties of the obtained polymercoating film easily becomes insufficient, and a too high molecularweight is apt to be disadvantageous from the viewpoint ofprocessability. Particularly in the case of aiming at forming a thincoating film by using the polymer as a coating material, a too highmolecular weight is disadvantageous from the viewpoint of film formingproperty. The molecular weight is preferably not more than 300,000,particularly preferably not more than 200,000.

The fluorine-containing polymers of the formulae (Ma), (Mb), (Ma-1) and(Mb-1) of the present invention can be obtained by various processes,for example, by copolymerizing, through known process, monomerscorresponding to the respective structural units, namely, thefluoroolefin (M1), the unsaturated compound having a monocyclicstructure or the diene compound (M2) being capable of undergoing cyclicpolymerization, the ethylenic monomer (N1) having functional group ascase demands and the monomer (N) corresponding to the optionalcomponent. For the polymerization, radical polymerization method, anionpolymerization method, cation polymerization method and the like can beemployed. Among them, the radical polymerization method is preferablyused from the point that each monomer for obtaining the polymer of thepresent invention has good radical polymerizability, control ofcomposition and molecular weight is easy and production in an industrialscale is easy.

Namely, in order to initiate the polymerization, means for initiation isnot limited particularly as far as the polymerization proceedsradically. The polymerization is initiated, for example, with an organicor inorganic radical polymerization initiator, heat, light, ionizingradiation or the like. The polymerization can be carried out by solutionpolymerization, bulk polymerization, suspension polymerization, emulsionpolymerization or the like. The molecular weight is controlled by thecontents of monomers to be used for the polymerization, the content ofpolymerization initiator, the content of chain transfer agent,temperature, etc. The components of the copolymer to be produced can becontrolled by the starting monomer components.

The second of the present invention relates to a novelfluorine-containing unsaturated aliphatic monocyclic compound havingfunctional group.

The novel fluorine-containing unsaturated cyclic compound of the presentinvention is a compound represented by the formula (1):

wherein Z³ are the same or different and each is —Rf³-Z⁴, in which Z⁴ isat least one functional group selected from the group consisting of OHgroup, COOH group, a derivative of carboxylic acid group and afunctional group protected by a protective group which can convert thefunctional group to OH group due to reaction with an acid; Rf³ is afluorine-containing alkylene group which has 1 to 30 carbon atoms andmay have ether bond; n11 is an integer of from 1 to 4.

The compound of the formula (1) of the present invention is afluorine-containing unsaturated cyclic compound having functional group,and the moiety Z³ having functional group and bonded to the cyclicstructure is characterized by having a fluorine-containing alkylenegroup Rf³, which is preferred because copolymerizability withfluoroolefins becomes better and transparency of the obtainedfluorine-containing polymer becomes excellent.

Examples of preferred functional group Z⁴ are the same as the examplesof the functional group Z¹ contained in the structural unit of theformula (b) in the above-mentioned fluorine-containing polymer.

Examples of preferred fluorine-containing alkylene group Rf³ are:

-   —(CF₂)_(n)—, —(CH₂)_(m)—(CF₂)_(n)— (m and n are integers of from 1    to 10),

and the like.

The first of the preferred fluorine-containing unsaturated cycliccompounds of the present invention is represented by the formula (2):

wherein Rf⁴ is a perfluoroalkylene group which has 1 to 10 carbon atomsand may have ether bond; R¹⁴ is hydrogen atom or an alkyl group having 1to 10 carbon atoms; n11 is as defined in the formula (1).Examples thereof are:

and the like.

Those unsaturated cyclic compounds may be synthesized by any processes.For example, synthesis can be carried out by the following process.

First, a halide X⁴—Rf⁴—COOR¹⁴, in which X⁴ is selected from bromine oriodine, is reacted at low temperature directly with a metal such aszinc, magnesium or Li or with an organometallic compound comprising theabove-mentioned metal such as a Grignard reagent or an alkyl lithiumcompound, thus preparing a fluorine-containing alkylation agentX⁴MRf⁴—COOR¹⁴, in which X⁴ is bromine or iodine, M is a metal.

Next, a halide of cyclopentene:

wherein X⁵ is selected from chlorine, bromine and iodine, is reacted atlow temperature with the previously prepared fluorine-containingalkylation agent X⁴MRf⁴—COOR¹⁴ and thereby a fluorine-containingcyclopentene compound having carboxylic acid or derivative of carboxylicacid corresponding thereto can be obtained.

The second of the preferred fluorine-containing unsaturated cycliccompound of the present invention is a cyclopentene compound having afluorine-containing alcohol structure which is represented by theformula (3):

wherein R¹⁵ is an alkylene group which has 1 to 5 carbon atoms and mayhave ether bond or a fluorine-containing alkylene group which has 1 to 5carbon atoms and may have ether bond; Rf⁵ is a fluorine-containing alkylgroup which has 1 to 10 carbon atoms and may have ether bond; Rf⁶ ishydrogen atom, an alkyl group having 1 to 10 carbon atoms or afluorine-containing alkyl group which has 1 to 10 carbon atoms and mayhave ether bond; n12 is 0 or 1; n11 is as defined in the formula (1).

Particularly preferred is a cyclopentene compound having afluorine-containing alcohol structure which is represented by theformula (4):

wherein Rf⁵ and Rf⁶ are as defined in the above-mentioned formula; n13is 0 or an integer of from 1 to 5; n14 is 0 or 1; n 1 is as defined inthe formula (1).

Further it is preferable that Rf⁵ and Rf⁶ are the same or different andeach is a perfluoroalkyl group having 1 to 5 carbon atoms.

Those cyclopentene compounds having a fluorine-containing alcoholstructure are particularly useful monomers for resist applicationbecause particularly high transparency can be imparted to the polymerobtained by copolymerization and solubility in a developing solution canalso be imparted because of high acidity of OH group.

Examples of those cyclopentene compounds having a fluorine-containingalcohol structure are:

and the like.

Those unsaturated cyclic compounds may be synthesized by any processes.For example, synthesis can be carried out by the following process.

First, a magnesium metal is reacted directly with a halide ofcyclopentene compound:

wherein X⁵ is selected from chlorine, bromine and iodine, to synthesizea cyclopentene magnesium halide (Grignard reagent) and then hexafluoroacetone is reacted therewith, and thus an unsaturated cyclic compoundcan be produced.

The third of the present invention relates to the photoresistcomposition, preferably the chemically amplifying photoresistcomposition which comprises a fluorine-containing aliphatic monocyclicpolymer having an acid-reactive group and a photoacid generator and canbe used for a patterning process using F₂ laser as light source.

The chemically amplifying photoresist comprises a resin (polymer)component and a photoacid generator. An acid is generated from the acidgenerator at an energy-exposed portion of the resist and a catalyticaction of the acid is used. In the chemically amplifying positivephotoresist, an acid generated at an energy-exposed portion is scatteredby the following heat-treatment (post exposure bake: hereinafterabbreviated to PEB) to release an acid-labile or acid-decomposablefunctional group of the resin and re-generate an acid, thereby makingthe energy-exposed portion soluble in alkali. The chemically amplifyingnegative photoresist generally has a functional group being capable ofundergoing condensation reaction by an acid and is alkali-soluble. Thenegative photoresist contains a crosslinking agent in addition to theresin component and acid generator.

The photoresist composition of the present invention (preferablychemically amplifying photoresist composition) can be used as theabove-mentioned positive type and negative type photoresists andcomprises:

-   (A-1) a fluorine-containing polymer having OH group, COOH group    and/or a group which can be dissociated by an acid and converted to    OH group or COOH group,-   (B) a photoacid generator and-   (C) a solvent,    in which the fluorine-containing polymer (A-1) is a polymer    comprising a structural unit derived from a fluoroolefin and a    structural unit derived from a monomer introducing an aliphatic    monocyclic structure in the polymer trunk chain, preferably, among    the above-mentioned polymers having an aliphatic monocyclic    structure in the polymer trunk chain, a fluorine-containing polymer    having, as a functional group, OH group, COOH group and/or a    functional group protected by a protective group which can convert    the functional group to OH group or COOH group by reaction with an    acid.

It has been considered that when a polymer having a monocyclic structurewas used for a resist, dry etching resistance was insufficient. Thepresent inventors have found that enough dry etching resistance can beobtained by copolymerizing a structural unit having a monocyclicstructure in its trunk chain with a fluoroolefin.

The fluorine-containing polymer (A-1) to be used in the photoresistcomposition of the present invention (preferably chemically amplifyingphotoresist composition) is selected from those having a functionalgroup working for a positive or negative resist among theabove-mentioned fluorine-containing polymers having functional group ofthe formula (Mb) and/or (Ma-1).

The functional group working for a resist represents OH group, COOHgroup, a functional group (—O—P) protected by a protective group (—P)which can convert the functional group to OH group by reaction with anacid or a functional group (—COO—P) protected by a protective group (—P)which can convert the functional group to COOH group by reaction with anacid, and at least one of them is selected.

Examples of the protected functional groups —O—P and —COO—P arepreferably the same as those described in the above-mentionedexplanation with respect to the functional group of thefluorine-containing polymer.

When the fluorine-containing polymer is used for the photoresistcomposition (preferably chemically amplifying photoresist composition),the content of the above-mentioned functional group in the polymer (whena plurality of functional groups are used, the sum thereof variesdepending on the polymer backbone and kind of the functional group andis from 5 to 80% by mole, preferably from 20 to 70% by mole, morepreferably from 30 to 60% by mole based on the whole structural units.When the content is too low, it is not preferred because solubility in adeveloping solution and resolution become insufficient. When the contentis too high, it is not preferred because transparency and dry etchingresistance are lowered.

The fluorine-containing polymer (A-1) to be used in the photoresistcomposition (preferably chemically amplifying photoresist composition)can be selected from the preferred examples of the above-mentionedfluorine-containing polymers (functional group is selected from thosementioned above).

As a result of further studies by the present inventors, it was foundthat a fluorine-containing polymer having a specific monocyclicstructure having hydroxyl (OH) group in trunk chain is well dissolved inan alkaline developing solution which is used in a developing step ofphotoresist process.

Also it was found that a composition comprising the abovefluorine-containing polymer or the fluorine-containing polymer havingprotected OH group and a photoacid generator is useful as a photoresistcomposition.

Namely, the fourth of the present invention relates to a photoresistcomposition which comprises:

-   (A-2) a fluorine-containing polymer having OH group which has    recurring units of an aliphatic monocyclic structure in the polymer    trunk chain, in which OH group or a moiety having OH group is bonded    to the carbon atom constituting the aliphatic monocyclic structure,-   (B) a photoacid generator and-   (C) a solvent,    in which when in the recurring units of aliphatic monocyclic    structure of the fluorine-containing polymer (A-2), the carbon atom    bonded to OH group is named the first carbon atom and a structure    consisting of the first carbon atom up to the neighboring fourth    carbon atom is assumed to be a model structure, the model structure    having OH group satisfies Equation 1:    ΔH=H(M-O⁻)+200−H(M-OH)≦75  (Equation 1),    preferably Equation 2:    ΔH=H(M-O⁻)+200−H(M-OH)≦70  (Equation 2)    wherein H(M-OH) is a produced enthalpy of the model structure,    H(M-O⁻) is a produced enthalpy of the model structure after    dissociation of the OH group and a produced enthalpy of hydrogen ion    is assumed to be a constant of 200 kJ/mol.

It has been generally said that with respect to a relation between anacidity and alkali solubility, when an acidity is increased, namely whenan acid dissociation constant pKa is decreased, alkali solubilitybecomes high. However, it is not always said that any of compositionshaving a smaller pKa have high solubility in alkali. For example,solubility of a resist in a developing solution is not determined onlyby pKa of a OH group-containing monomer.

For example, a pKa value of OH group of phenol which is a representativeexample of hydrocarbon compound having OH group is 10 and solubility ina developing solution is good. However among fluorine-containingpolymers obtained by copolymerizing a OH group-containing monomer havinga pKa value of about 10, there are some polymers insoluble in adeveloping solution.

As mentioned above, it has been difficult to select a compound having anoptimum solubility in a developing solution only by a pKa value.

The present inventors have made another approach to the above-mentionedproblem taking account of produced energy of OH group before and afterthe acid dissociation and have found that a fluorine-containing polymerhaving OH group which has, in its trunk chain, recurring unitssatisfying a specific equation of ΔH (difference in produced energy)defined above has unexpectedly excellent solubility in a developingsolution. This equation of ΔH mentioned above was firstly found by thepresent inventors.

Conventional hydrocarbon compounds having OH group have a pKa value ofnot less than 12, generally from 14 to 16. However those hydrocarboncompounds do not have enough correlation between the above-mentioneddifference in produced enthalpy (ΔH) of OH group before and after thedissociation and the actually measured pKa value.

As mentioned above, the present inventors actually measured pKa valuesof various fluorine-containing compounds having OH group and on theother hand, suggested the above-mentioned ΔH. As a result ofinvestigation with respect to a relation between the ΔH and the actuallymeasured pKa value, the present inventors have found that the pKa valueof particularly a fluorine-containing compound having OH group which hasa pKa value of not more than 12 has a good proportional relation withthe ΔH, and further have found that a pKa value of OH group of afluorine-containing compound having OH group can be conjectured bycalculating ΔH of the compound according to the equation (Equation 1 orEquation 2).

When paying attention to application as a polymer for a resist, it isnecessary for the polymer to have high solubility in an alkalinedeveloping solution such as an aqueous solution of 2.38% by weight oftetramethylammonium hydroxide which is generally used in a developingstep. On the other hand, in F2 resist application, transparency at 157nm in a vacuum ultraviolet region is required and the use of carboxylgroup and phenolic hydroxyl group which have been used for conventionalresists as a group soluble in a developing solution is disadvantageousfrom the viewpoint of transparency. Therefore, in the polymer structure,it is necessary to select a structure including OH group and itsneighboring structure which gives high transparency and excellentsolubility in a developing solution.

Hitherto studies have been made with respect to the use of afluorine-containing polymer to which a norbornene backbone having—C(CF₃)₂OH group as a group soluble in a developing solution isintroduced, as a polymer for F2 resist possessing improved transparencyand solubility in a developing solution (WO00/67072, etc.). Howeverthough the OH group of this fluorine-containing polymer has solubilityin a developing solution by an effect of two CF₃ groups, a dissolvingrate of the polymer itself is insufficient only by the introduction of—C(CF₃

₂OH.

The present inventors have studied various fluorine-containing monomershaving OH group and structural units derived therefrom taking advantageof the above-mentioned relation between AH and pKa value. As a result,the present inventors defined a model structure of not only —C(CF₃)₂OHportion but also its neighboring structure and calculated ΔH thereof andhave found that when the ΔH is not more than a specific value, thepolymer possesses good solubility in a developing solution.

Based on those new findings, further studies have been made, and it wasfound that the fluorine-containing polymer having, in the polymer trunkchain, recurring units of aliphatic monocyclic structure having OH groupwhich satisfies the above-mentioned equation of ΔH (Equation 1 orEquation 2) or the fluorine-containing polymer having a functional groupprotecting the OH group is excellent in solubility in a developingsolution while maintaining excellent transparency as the resist polymer.

Next, a method of calculating a difference AH in produced energy beforeand after acid dissociation in the present invention is explained below.

First, the aliphatic monocyclic structural unit having OH group in thepolymer is selected. Provided that the carbon atom bonded to OH group ofthe aliphatic monocyclic structural unit is the first carbon atom,attention is paid only to the neighboring carbon atoms and the carbonatom adjacent to the first carbon atom is assumed to be the secondcarbon atom and the carbon atom adjacent to the second carbon atom isassumed to be the third carbon atom. A structure up to the fourth carbonatom is selected. If an atomic valence on the fourth carbon atom isinsufficient, a structure subjected to replacement with hydrogen atom isassumed to be the model structure. When the number of carbon atomsconstituting the aliphatic monocyclic structural unit is few and thefourth carbon atom is not present, the aliphatic monocyclic structuralunit is assumed to be a model structure.

The reason why the structure up to the fourth carbon atom is assumed tobe the model structure is that even if a structure including the fifthor more carbon atoms which are far from OH is considered, it does nothave an effect greatly on the ΔH value, and for comparing ΔH, thestructure up to the fourth carbon atom suffices. Also in case of a largemodel structure, there arises a problem that a sufficient accuracy isdifficult to obtain by a software of calculation method of molecularorbital available on the market, which is not preferable.

If technical problems of the calculation are solved, the ΔH value of thewhole fluorine-containing monomer having the aliphatic monocyclicstructure may be calculated without using the model structure.

For example, in the case of a structure which is represented by theformula:

when the carbon atoms are numbered, the structure is represented by:

and the structure including carbon atoms up to the fourth carbon atom(C⁴) constitutes a ring. A structure having hydrogen atoms bonded to thecarbon atoms (C³ and C⁴) having insufficient atomic valence is used asthe model structure.

Then the calculation of molecular orbital of the adopted model structureis first carried out to calculate a produced enthalpy: H(M-OH) beforethe acid dissociation.

Each produced enthalpy is calculated using the semi-empiricalcalculation method of molecular orbital: AM1 method (described inJournal of American Chemical Society, 107, p 3902 (1985) by M. J. S.Dewar, E. G. Zoebisch, E. F. Heary and J. J. P. Stewart,). In thepresent invention, the calculation is carried out using MOPACcalculation software MOPAC97 (software for calculation of molecularorbital) available from FUJITSU LIMITED which uses CS Chem3D(R) Version4.0 available from Cambridge Soft Corporation.

With respect to the same model structure in which OH has beendissociated, a produced enthalpy H(M-O⁻) after the acid dissociation iscalculated by the same method as above. The produced enthalpy ofhydrogen ion is set at 200 kJ/mol as a constant.

The ΔH values of the respective aliphatic monocyclic structures (modelstructure) having OH group in the fluorine-containing polymer aredetermined unambiguously by the above-mentioned calculation.

It is a surprise that the above-mentioned Equation 1 and Equation 2 canbe applied on the fluorine-containing polymer having, in its trunkchain, a structural unit derived from a fluorine-containing ethylenicmonomer having OH group and also the fluorine-containing polymer having,in its trunk chain, a structural unit derived from a fluorine-containingnorbornene derivative.

In the case of the fluorine-containing polymer prepared bycopolymerizing a fluorine-containing ethylenic monomer having OH group,the model structure thereof is determined by the following method.

Provided that the carbon atom bonded to OH group is the first carbonatom, attention is paid only to the neighboring carbon atoms and thecarbon atom adjacent to the first carbon atom is assumed to be thesecond carbon atom and the carbon atom adjacent to the second carbonatom is assumed to be the third carbon atom. A structure up to the thirdor the fourth carbon atom is selected. If an atomic valence on the thirdor the fourth carbon atom is insufficient, a structure subjected toreplacement with hydrogen atom is assumed to be the model structure.

The reason why the structure up to the fourth carbon atom at maximum isassumed to be the model structure is the same as mentioned above. Iftechnical problems of the calculation are solved, the ΔH value of thewhole fluorine-containing ethylenic monomer may be calculated withoutusing the model structure, which is also as mentioned above. However ifthe number of fluorine atoms in the structure increases, accuracy of theMOPAC calculation (explained infra) is lowered. Therefore, when thenumber of fluorine atoms in the model structure up to the fourth carbonis not less than seven, it is preferable that the calculation is carriedout using a structure up to the third carbon as the model structure.

For example, in the case of a fluorine-containing ethylenic monomerhaving OH group which is represented by the formula:CH₂═CHCH₂C(CF₃)₂OH,when the carbon atoms are numbered, the monomer is represented by:C⁴H₂═C³HC²H₂C¹(C²F₃)₂OHand the structure including carbon atoms up to the fourth carbon atom(C⁴) and having six or less fluorine atoms can be used for thecalculation. Therefore the whole molecular structure CH₂═CHCH₂C(CF₃)₂OHis used for the calculation.

Also in the case of the following fluorine-containing ethylenic monomer:

when carbon atoms up to the fourth carbon atom (C⁴) are used, the numberof fluorine atoms is not less than seven. Therefore the model structureup to the third carbon atom (C³), namely:

is used for the calculation of the structural unit derived from thefluorine-containing ethylenic monomer having OH group.

Next, in the case of a fluorine-containing polymer having a structuralunit derived from a fluorine-containing norbornene derivative in itstrunk chain, the model structure is basically selected according to thesame definition as in the aliphatic monocyclic structural unit.

For example, in the case of:

when carbon atoms up to the fourth one is used, the model structure ofthe structural unit derived from a fluorine-containing norbornenederivative is represented by:

and, the structure subjected to bonding of hydrogen to the carbon (C⁴)due to insufficient atomic valence can be used as the model structure.

In this case, too, if technical problems of the calculation are solvedbecause a percentage of replacement with fluorine atom is small, the ΔHvalue of the whole structural unit derived from a fluorine-containingnorbornene derivative may be calculated.

The fluorine-containing polymer (A-2) for the photoresist composition ofthe present invention has a structural unit having not more than 75kJ/mol of the ΔH value calculated by the above-mentioned method amongthe aliphatic monocyclic structures (model structure) having OH group.This polymer is preferable as a photoresist being excellent intransparency and being high in solubility in an aqueous solution(developing solution) of 2.38% by weight of tetramethylammoniumhydroxide in which fluorine-containing polymers have been said to behardly dissolved.

The ΔH value is preferably not more than 70 kJ/mol, more preferably notmore than 50 kJ/mol. When the ΔH value is too large, solubility in adeveloping solution of the polymer obtained by polymerization becomesinsufficient, and at forming a resist pattern, a sufficient resolutionis not obtained, a fine pattern is not obtained and scum and residueeasily remain in the resist. A lower limit of the ΔH value is −110kJ/mol, preferably not less than −65 kJ/mol, more preferably not lessthan −40 kJ/mol.

The photoresist composition of the fifth of the present invention is aphotoresist composition which comprises:

-   (A-3) a fluorine-containing polymer having OH group which has    recurring units of an aliphatic monocyclic structure in the polymer    trunk chain, in which OH group or a moiety having OH group is bonded    to the carbon atom constituting the aliphatic monocyclic structure,-   (B) a photoacid generator and-   (C) a solvent,    in which the recurring units of the aliphatic monocyclic structure    of the fluorine-containing polymer (A-3) have a structure    represented by the formula (50):

wherein Rf¹¹ is a perfluoroalkyl group having 1 to 20 carbon atoms; Z¹⁰is fluorine atom or a perfluoroalkyl group having 1 to 20 carbon atoms.

The fluorine-containing polymer (A-3) having such a structure of theformula (50) exhibits better solubility in an aqueous solution of 2.38%by weight of tetramethylammonium hydroxide which is generally used as adeveloping solution for a resist, because of effects of Rf¹¹ and inaddition, the group Z¹⁰ bonded to the neighboring carbon atom of thecarbon atom bonded to Rf¹¹ and therefore, is preferred as a resistpolymer.

In the structure of the formula (50), Rf¹¹ is a perfluoroalkyl group andexamples thereof are

F(CF₂)_(n1) (n1 is an integer of from 1 to 20),

(n2 is an integer of from 1 to 6) and

(n3 and n4 are integers which make the sum of carbon atoms being notmore than 20), and among them, CF₃, C₂F₅, C₃F₇, C₄F₉, (CF₃)₂CF and thelike are preferred.

In the structure of the formula (50), Z¹⁰ is selected from fluorine atomor a perfluoroalkyl group having 1 to 20 carbon atoms. Examples ofpreferred perfluoroalkyl group are the same as those of Rf¹¹, andparticularly preferred are F, CF₃ and C₂F₅.

The structure of the formula (50) may be present in the form of a sidechain on the aliphatic monocyclic structure constituting thefluorine-containing polymer (A-3) or in the form of a part of the ringstructure forming the aliphatic monocyclic structure. Also at least oneOH group may be present in one molecule of the monocyclic structure, andthe aliphatic monocyclic structure may have two or more OH groups.

Example of the preferred structure of the formula (50) in the recurringunits of aliphatic monocyclic structure of the fluorine-containingpolymer (A-3) is a structure represented by the formula (51):

wherein Rf¹¹ and Rf¹² are the same or different and each is aperfluoroalkyl group having 1 to 20 carbon atoms; Z¹⁰ is fluorine atomor a perfluoroalkyl group having 1 to 20 carbon atoms.

In the structure of the formula (51), examples of the Rf¹² arepreferably the same as those of the Rf¹¹. Rf¹¹ and Rf¹² may be the sameor different.

Also the structure of the formula (51) may be present in the form of aside chain on the aliphatic monocyclic structure constituting thefluorine-containing polymer (A-3) or in the form of a part of the ringstructure forming the aliphatic monocyclic structure. At least one OHgroup may be present in one molecule of the monocyclic structure, andthe aliphatic monocyclic structure may have two or more OH groups.

Also preferable example of the structure of the formula (50) in therecurring units of aliphatic monocyclic structure of thefluorine-containing polymer (A-3) is a structure represented by theformula (52):

wherein Rf¹¹ is a perfluoroalkyl group having 1 to 20 carbon atoms; Z¹⁰and Z¹¹ are the same or different and each is fluorine atom or aperfluoroalkyl group having 1 to 20 carbon atoms.

In the structure of the formula (52), examples of the Z¹¹ are preferablythe same as those of the above-mentioned Z¹⁰. Z¹⁰ and Z¹¹ may be thesame or different.

Also the structure of the formula (52) may be present in the form of aside chain on the aliphatic monocyclic structure constituting thefluorine-containing polymer (A-3) or in the form of a part of the ringstructure forming the aliphatic monocyclic structure. At least one OHgroup may be present in one molecule of the monocyclic structure, andthe aliphatic monocyclic structure may have two or more OH groups.

In the fluorine-containing polymer having the structure of the formula(50), (51) or (52), though the ΔH value of the structure may exceed 75kJ/mol, many structural units having the ΔH value of not more than 75kJ/mol are contained in the polymer and as a matter of course, the ΔHvalue of the polymer is preferably not more than 75 kJ/mol, morepreferably not more than 70 kJ/mol, particularly preferably not morethan 50 kJ/mol.

Example of the preferred structure of the recurring unit of thealiphatic monocyclic structure contained in the fluorine-containingpolymer which is used for the photoresist composition of the presentinvention is the structural unit of the formula (53):

wherein Rf⁵⁰ and Rf⁵¹ are the same or different and each is aperfluoroalkyl group having 1 to 20 carbon atoms; X¹⁰ and X¹¹ are thesame or different and each is H, F, an alkyl group having 1 to 20 carbonatoms, preferably 1 to 5 carbon atoms or a fluorine-containing alkylgroup which has 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms andmay have ether bond; X¹² is hydrogen atom, fluorine atom, an alkyl grouphaving 1 to 20 carbon atoms, a fluorine-containing alkyl group which has1 to 20 carbon atoms and may have ether bond, OH group or a grouprepresented by the formula:

wherein Rf⁵² and Rf⁵³ are the same or different and each is aperfluoroalkyl group having 1 to 20 carbon atoms; R⁵⁰ is at least oneselected from an alkylene group or fluorine-containing alkylene groupwhich has 1 to 3 carbon atoms and constitutes a ring; R⁵¹ and R⁵² arethe same or different and each is at least one selected from a divalenthydrocarbon group which has 1 to 7 carbon atoms and constitutes a ring,oxygen atom, a divalent hydrocarbon group having ether bond which hasthe sum of oxygen atoms and carbon atoms of 2 to 7 and constitutes aring, a divalent fluorine-containing alkylene group which has 1 to 7carbon atoms and constitutes a ring or a divalent fluorine-containingalkylene group having ether bond which has the sum of oxygen atoms andcarbon atoms of 2 to 7 and constitutes a ring; and the sum of carbonatoms constituting a trunk chain in R⁵¹ and R⁵² is not more than 7, andOH group or a group represented by the formula:

wherein Rf⁵² and Rf⁵³ are as defined above, may be bonded to any ofcarbon atoms in R⁵¹; R⁵³ and R⁵⁴ are the same or different and each is adivalent alkylene group having 1 or 2 carbon atoms or a divalentfluorine-containing alkylene group having 1 or 2 carbon atoms; n50, n51,n52, n53 and n54 are the same or different and each is 0 or 1,or the structural unit represented by the formula (54):

wherein Rf⁵⁰, X¹⁰, X¹¹, R⁵⁰R⁵¹, R⁵², R⁵³, R⁵⁴, n50, n51, n52, n53 andn54 are as defined in the above-mentioned formula (53). Thefluorine-containing polymer having the structural unit (53) or (54) isreferred to as (A-5).

Also it is preferable that the structural unit (53) or (54) contains anyof the above-mentioned structures of the formula (50), (51) and (52).

Concretely it is preferable that X¹² in the formula (53) is Z¹⁰ in theformula (51), wherein Z¹⁰ is fluorine atom or a perfluoroalkyl grouphaving 1 to 20 carbon atoms.

It is preferable that at least one Z¹⁰ of the formula (50), wherein Z¹⁰is fluorine atom or a perfluoroalkyl group having 1 to 20 carbon atoms,is bonded to any one of neighboring carbon atoms of the carbon atombonded to OH group of the formula (54) or it is preferable that one ortwo of Z¹⁰ and of Z¹¹ of the formula (52), wherein Z¹⁰ and Z¹¹ are thesame or different and each is fluorine atom or a perfluoroalkyl grouphaving 1 to 20 carbon atoms, are bonded to both neighboring carbon atomsof the carbon atom bonded to OH group of the formula (54).

Those fluorine-containing polymers having recurring unit of monocyclicstructure represented by the formula (53) or (54) are novel substanceswhich have not been disclosed in prior literatures and patentpublications. Also the above-mentioned preferred structural units of theformula (53) and (54) are novel substances which have not been disclosedin prior literatures and patent publications.

More concretely examples thereof are those mentioned below, andcalculated ΔH values of some of them are also mentioned below.

Also in the photoresist composition of the present invention, two ormore OH groups or moieties having OH group may be bonded in thealiphatic monocyclic structure having OH group. For example, preferredis the monocyclic structure of the formula (53), in which a group:

wherein Rf⁵² and Rf⁵³ are the same or different and each is aperfluoroalkyl group having 1 to 20 carbon atoms, is bonded instead ofX¹², and/or at least one group:

wherein R⁵² and R⁵³ are as defined above, is bonded to any of carbonatoms of R⁵¹ (in case where n51 is 1). Also preferred is the monocyclicstructural unit of the formula (54), in which OH group is bonded to anyof carbon atoms of R⁵¹ (in case where n51 is 1) and/or at least onestructural unit:

wherein R⁵² is as defined above, is contained in the structure of R⁵¹(in case where n51 is 1).

Examples thereof are:

and the like. It is preferable that the fluorine-containing polymer hasthose structural units. The fluorine-containing polymers havingrecurring units of those monocyclic structures are novel substanceswhich have not been disclosed in any of literatures and patentpublications.

Among them, a monomer:

which can introduce a structural unit:

is also a novel compound. Example of a preparation process thereof is asshown in the following preparation scheme (1).

Also a monomer:

which can introduce a structural unit:

is a novel compound. Example of a preparation process thereof is asshown in the following preparation scheme (2).

Also a monomer:

which can introduce a structural unit:

is a novel compound. Example of a preparation process thereof is asshown in the following preparation scheme (3).

(MEC-31 is a fluorinating agent available from DAIKIN INDUSTRIES, LTD.)

Also a monomer represented by:

which can introduce a structural unit represented by:

is a novel compound, and example of a preparation process thereof is thefollowing preparation scheme (4).

(MEC-11 is a fluorinating agent available from DAIKIN INDUSTRIES, LTD.)

Also a structural unit represented by:

can be obtained by cyclic polymerization of a diene compound representedby:

and further can be obtained by (co)polymerization of a novel monomerrepresented by:

and example of a preparation process thereof is the followingpreparation scheme (5).Preparation Scheme (5)

It is preferable that the fluorine-containing polymer having OH groupfor the photoresist composition of the present invention has at leastone of the aliphatic monocyclic structure satisfying the above-mentionedEquation 1, aliphatic monocyclic structures having the structures of theformulae (50) to (52) or the monocyclic structures of the formula (53)to (54) (which are generically referred to as “structural unit M3”). Thefluorine-containing polymer is a homopolymer consisting of thestructural unit M3 of monocyclic structure having OH group or acopolymer comprising the structural unit M3 and a structural unitcopolymerizable therewith (the above-mentioned M1, N, etc.). Concretelyit is preferable that the fluorine-containing polymer is afluorine-containing polymer having a number average molecular weight offrom 500 to 1,000,000 which is represented by the formula (60):-(M3)-(N3)-  (60)wherein M3 is at least one recurring unit selected from recurring unitsof the aliphatic monocyclic structure satisfying the above-mentionedEquation 1 or 2, aliphatic monocyclic structures having the structuresof the formula (50) to (52) or the monocyclic structures of the formula(53) to (54); N3 is a structural unit derived from a monomercopolymerizable with the monomer to introduce the structural unit M3,andthe structural units M3 and N3 are contained in amounts of from 0.1 to100% by mole and from 0 to 99.9% by mole, respectively.

Particularly the fluorine-containing polymer having the recurring unitselected from the monocyclic structures of the formula (53) to (54) is anovel substance which has not been disclosed in literatures and patentpublications.

Namely, the novel fluorine-containing polymer of the present inventionis a fluorine-containing polymer having a number average molecularweight of from 500 to 1,000,000 which is represented by the formula(61):-(M3-1)-(N-3-1)-  (61)wherein M3-1 is at least one structural unit selected from themonocyclic structural units of the formulae (53) and (54); N3-1 is astructural unit derived from a monomer copolymerizable with the monomerto introduce the structural unit M3-1, andthe structural units M3-1 and N3-1 are contained in amounts of from 0.1to 100% by mole and from 0 to 99.9% by mole, respectively.

Examples of the structural unit M3-1 of the fluorine-containing polymerof the present invention are the same as those mentioned above aspreferred examples of the formulae (53) and (54).

In the formulae (60) and (61), the copolymerizable components N3 andN3-1 are optional components and are not particularly limited as far asthey are monomers copolymerizable with the structural units M3 and M3-1.The structural units N3 and N3-1 may be optionally selected depending onrequired characteristics of intended fluorine-containing polymer.

It is particularly preferable that the structural unit N3 or N3-1 is thestructural unit M1 in the above-mentioned novel fluorine-containingpolymer (Ma) (the structural unit derived from an ethylenic monomerhaving 2 or 3 carbon atoms and at least one fluorine atom), and examplesthereof are preferably the same as the above-mentioned preferredexamples of the structural unit M1. When those structural units areused, a polymer which has excellent transparency and dry etchingresistance and is preferred as a photoresist polymer can be obtained.

Examples of the structural unit N3 are preferably the same as theabove-mentioned examples of the structural units N and N1 (examplesmentioned in (i) and (ii) of the structural unit N and examples of N1)explained in the first of the present invention (fluorine-containingpolymer having an aliphatic monocyclic structure in its trunk chain).

In the fluorine-containing polymer of the present invention(fluorine-containing polymer used for a photoresist composition),various combinations and proportions of the structural unit M3 or M3-1and the structural unit N3 or N3-1 can be selected from theabove-mentioned examples depending on intended application, physicalproperties (particularly glass transition point, hardness, etc.),functions (transparency, refractive index), etc.

One of the fluorine-containing polymers of the present invention(fluorine-containing polymers used for a photoresist composition)contains the structural unit M3 or M3-1 as an essential component andhas functions due to the structural unit M3 or M3-1 itself such asmaintaining a low refractive index and imparting transparency to thepolymer, and functions due to hydroxyl such as imparting solubility in asolvent, solubility in an aqueous alkaline solution (developingsolution), adhesion to a substrate and crosslinkability because OH groupand fluorine atom can be introduced to the cyclic structural unit. Inaddition, dry etching resistance also becomes good because of the cyclicstructural unit. Therefore even if the fluorine-containing polymer ofthe present invention contains a larger amount of the structural unit M3or M3-1 or in the extreme case, even if the polymer consists of thestructural unit M3 or M3-1 (100% by mole), transparency and the dryetching resistance can be maintained.

Further in the case of the copolymer of the present invention comprisingthe structural unit M3 or M3-1 and the structural unit N3 or N3-1 of acopolymerizable monomer, when the structural unit N3 or N3-1 is selectedfrom the above-mentioned examples, a fluorine-containing polymer havinga higher glass transition point, a higher transparency (particularly ina vacuum ultraviolet region) and a higher dry etching resistance can beobtained.

In the copolymer comprising the structural unit M3 or M3-1 and thestructural unit N3 or N3-1, the proportion of the structural unit M3 orM3-1 may be not less than 0.1% by mole based on the whole monomersconstituting the fluorine-containing polymer. In order to impartsolubility in an alkaline solution (developing solution) to thefluorine-containing polymer, it is preferable that the structural unitM3 or M3-1 is contained in an amount of not less than 10% by mole,preferably not less than 20% by mole, more preferably not less than 30%by mole. An upper limit thereof is (not more than) 100% by mole.

The fluorine-containing polymer of the present invention(fluorine-containing polymer used for a photoresist composition) ispreferable particularly for the resist application since transparencyand dry etching resistance are not lowered even if the proportion of thestructural unit M3 or M3-1 is increased.

Also in the case of the above-mentioned application requiringtransparency, preferred combinations and proportions of the structuralunit M3 or M3-1 and the structural unit N3 or N3-1 are those which canmake the fluorine-containing polymer non-crystalline.

The molecular weight of the fluorine-containing polymer of the presentinvention (fluorine-containing polymer used for a photoresistcomposition) can be selected, for example, within a range of from 500 to1,000,000 in number average molecular weight. Preferred molecular weightis from 1,000 to 500,000, particularly from 2,000 to 200,000.

When the molecular weight is too low, mechanical properties easilybecome insufficient, and the resist film is apt to be insufficient instrength. If the molecular weight is too high, solubility in a solventis lowered, and film forming property and leveling property are easilylowered particularly at forming a thin coating film. For coatingapplications, most preferable number average molecular weight isselected within a range of from 5,000 to 100,000.

With respect to transparency, it is preferable that the polymer istransparent in the case of vacuum ultraviolet light having a wavelengthof not more than 200 nm. For example, an absorption coefficient at 157nm is not more than 3.0 μm⁻¹, preferably not more than 2.0 μm⁻¹,particularly preferably not more than 1.0 μm⁻¹. Such afluorine-containing polymer is preferable as a base polymer for a F₂resist.

Also it is preferable that the fluorine-containing polymer is soluble ingeneral-purpose solvents, for example, in at least one of ketonesolvents, acetic acid ester solvents, alcohol solvents, aromaticsolvents, glycol ether solvents or glycol ester solvents or in a solventmixture containing at least one of the above-mentioned general-purposesolvents.

The fluorine-containing polymer of the present invention(fluorine-containing polymer used for a photoresist composition) can beobtained by polymerizing a monomer capable of introducing the structuralunit M3 or M3-1, for example, an unsaturated compound containing analiphatic monocyclic structure having OH group, by cyclic(co)polymerization of an ethylenic diene monomer having OH group or by(co)polymerizing, through known method, a monomer capable of introducingthe structural unit M3 or M3-1 and a monomer which is a copolymerizablecomponent as the structural unit N3 or N3-1. For the polymerization,radical polymerization method, anion polymerization method, cationpolymerization method and the like can be employed. Among them, theradical polymerization method is preferably used from the point thateach monomer exemplified to obtain the fluorine-containing polymerhaving OH group of the present invention has good radialpolymerizability, control of composition and molecular weight is easyand production in an industrial scale is easy.

In order to initiate the radical polymerization, means for initiation isnot limited particularly as far as the polymerization proceedsradically. The polymerization is initiated, for example, with an organicor inorganic radical polymerization initiator, heat, light, ionizingradiation or the like. The polymerization can be carried out by solutionpolymerization, bulk polymerization, suspension polymerization, emulsionpolymerization or the like. The molecular weight is controlled by thecontents of monomers to be used for the polymerization, the content ofpolymerization initiator, the content of chain transfer agent,temperature, etc. The components of the copolymer can be controlled bythe starting monomer components.

Further in the fluorine-containing polymer which is used for thephotoresist composition of the present invention, a part or the whole ofOH groups may be protected by a protective group which can undergoconversion to OH group by reaction with an acid. The protective groupundergoes conversion to OH group by an acid generated from a photoacidgenerator and thereby the polymer can work as a positive type resist.

Namely, the present invention relates to the photoresist compositionwhich comprises:

-   (A-4) a fluorine-containing polymer having functional group    protected by a protective group which can convert the functional    group to OH group by reaction with an acid,-   (B) a photoacid generator and-   (C) a solvent,    in which the fluorine-containing polymer (A-4) is a    fluorine-containing polymer having functional group comprising OH    group contained in the recurring unit of aliphatic monocyclic    structure of any of the above-mentioned fluorine-containing polymers    (A-2), (A-3) and (A-5) and the protective group protecting the OH    group.

Examples of the preferred acid-labile group which is used as aprotective group are groups represented by:

wherein R¹, R², R³ and R⁴ are the same or different and each is an alkylgroup having 1 to 5 carbon atoms.

More concretely there are preferably:

and from the viewpoint of good acid-reactivity, preferred are

and from the viewpoint of good transparency, preferred are —OC(CH₃)₃,—OCH₂OCH₃ and —OCH₂OC₂H₅.

The fluorine-containing polymer having only OH group can be used as anegative type resist in combination with a known crosslinking agent.

Also in the case of use for a positive type resist, when OH is presenttogether with another acid-labile group, for example, a functional groupwhich is converted to COOH group due to action of an acid, solubility ina developing solution and a dissolving rate can be adjusted andresolution can be enhanced.

Also the introduction of OH group and COOH group to thefluorine-containing polymer is preferred since adhesion to a substratecan be improved.

In the photoresist composition of the present invention (preferably achemically amplifying photoresist composition), the photoacid generator(B) is a compound which generates acid or cation by irradiating thephotoacid generator itself or the photoresist composition containing thephotoacid generator with radiation. The photoacid generators can be usedin a mixture of two or more thereof.

Examples of the photoacid generator (B) are, for instance, knowncompounds such as an organic halogen compound, sulfonic acid ester,onium salt, diazonium salt, disulfone compound and a mixture thereof.

Examples thereof are, for instance, haloalkyl group-containings-triazine derivatives such as tris(trichloromethyl)-s-triazine,tris(tribromomethyl)-s-triazine, tris(dibromomethyl)-s-triazine and2,4-bis(tribromomethyl)-6-p-methoxyphenyl-s-triazine,halogen-substituted paraffin hydrocarbons such as1,2,3,4-tetrabromobutane, 1,1,2,2-tetrabromoethane, carbon tetrabromideand iodoform, halogen-substituted cycloparaffin hydrocarbons such ashexabromocyclohexane, hexachlorocyclohexane and hexabromocyclododecane,haloalkyl group-containing benzene derivatives such asbis(trichloromethyl)benzene and bis(tribromomethyl)benzene, haloalkylgroup-containing sulfone compounds such as tribromomethylphenyl sulfoneand trichloromethylphenyl sulfone, halogen-containing sulfolanecompounds such as 2,3-dibromosulfolane, haloalkyl group-containingisocyanurates such as tris(2,3-dibromopropyl)isocyanurate, sulfoniumsalts such as triphenylsulfonium chloride, triphenylsulfoniummethanesulfonate, triphenylsulfoniumtrifluoromethane sulfonate,triphenylsulfonium-p-toluene sulfonate, triphenylsulfoniumtetrafluoroborate, triphenylsulfoniumhexafluoro arcenate andtriphenylsulfoniumhexafluoro phosphonate, iodonium salts such asdiphenyl-iodonium-trifluoromethane-sulfonate,diphenyl-iodonium-p-toluene-sulfonate, diphenyliodoniumtetrafluoroborate, diphenyliodonium hexafluoroarcenate anddiphenyliodonium hexafluorophosphonate, sulfonic acid esters such asmethyl p-toluenesulfonate, ethyl p-toluenesulfonate, butylp-toluenesulfonate, phenyl p-toluenesulfonate,1,2,3-tris(p-toluenesulfonyloxy)benzene, p-toluenesulfonic acid benzoinester, methyl methanesulfonate, ethyl methanesulfonate, butylmethanesulfonate, 1,2,3-tris(methanesulfonyloxy)benzene, phenylmethanesulfonate, methane sulfonic acid benzoin ester, methyltrifluoromethanesulfonate, ethyl trifluoromethanesulfonate, butyltrifluoromethanesulfonate,1,2,3-tris(trifluoromethanesulfonyloxy)benzene, phenyltrifluoromethanesulfonate and benzoin trifluoromethanesulfonate,disulfones such as diphenyldisulfone, sulfonediazides such asbis(phenylsulfonyl)diazomethane,bis(2,4-dimethylphenylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane,cyclohexylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(4-methoxyphenylsulfonyl)diazomehtane,cyclopentylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2-fluorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(3-fluorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(4-fluorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2-fluorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(3-fluorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(4-fluorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2-chlorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(3-chlorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(4-chlorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2-chlorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(3-chlorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(4-chlorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2-trifluoromethyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(3 -trifluoromethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(4-trifluoromethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2-trifluoromethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(3-trifluoromethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(4-trifluoromethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane,phenylsulfonyl-(2-methoxylphenylsulfonyl)diazomethane,phenylsulfonyl-(3-methoxylphenylsulfonyl)diazomethane,phenylsulfonyl-(4-methoxylphenylsulfonyl)diazomethane,bis(2-methoxylphenylsulfonyl)diazomethane,bis(3-methoxylphenylsulfonyl)diazomethane,bis(4-methoxylphenylsulfonyl)diazomethane,phenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane,phenylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane,phenylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane,phenylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane,2,4-dimethylphenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane,2,4-dimethylphenylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane,phenylsulfonyl-(2-fluorophenylsulfonyl)diazomethane,phenylsulfonyl-(3-fluorophenylsulfonyl)diazomethane andphenylsulfonyl-(4-fluorophenylsulfonyl)diazomethane, o-nitrobenzylesters such as o-nitrobenzyl-p-toluenesulfonate, sulfone hydrazides suchas N,N′-di(phenylsulfonyl)hydrazide and the like.

Examples of the preferable photoacid generator are compounds generatingany of sulfonic acid, sulfenic acid or sulfinic acid. Examples thereofare onium sulfonates such as triphenylsulfonium-p-toluenesulfonate anddiphenyliodonium-p-toluenesulfonate, sulfonic acid esters such as phenylp-toluenesulfonate and 1,2,3-tris(p-toluenesulfonyloxy)benzene,disulfones such as diphenyldisulfone, sulfonediazides such asbis(phenylsulfonyl)diazomethane,bis(2,4-dimethylphenylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane,cyclohexylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(4-methoxyphenylsulfonyl)diazomehtane,cyclopentylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2-fluorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(3-fluorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(4-fluorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2 -fluorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(3-fluorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(4-fluorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2-chlorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(3-chlorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(4-chlorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2-chlorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(3-chlorophenylsulfonyl)diazomethane,cyclopentylsulfonyl-(4-chlorophenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2-trifluoromethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(3-trifluoromethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(4-trifluoromethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2-trifluoromethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(3-trifluoromethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(4-trifluoromethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane,cyclohexylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane,cyclopentylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane,phenylsulfonyl-(2-methoxylphenylsulfonyl)diazomethane,phenylsulfonyl-(3-methoxylphenylsulfonyl)diazomethane,phenylsulfonyl-(4-methoxylphenylsulfonyl)diazomethane,bis(2-methoxylphenylsulfonyl)diazomethane,bis(3-methoxylphenylsulfonyl)diazomethane,bis(4-methoxylphenylsulfonyl)diazomethane,phenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane,phenylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane,phenylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane,phenylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane,2,4-dimethylphenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane,2,4-dimethylphenylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane,phenylsulfonyl-(2-fluorophenylsulfonyl)diazomethane,phenylsulfonyl-(3-fluorophenylsulfonyl)diazomethane andphenylsulfonyl-(4-fluorophenylsulfonyl)diazomethane, o-nitrobenzylesters such as o-nitrobenzyl-p-toluenesulfonate, and the like.Particularly sulfonediazides are preferable.

Further in addition to the above-mentioned examples, a photoacidgenerator of onium salts having fluorine atom can be used. For example,there are preferably used a fluoroalkyl onium salt represented by theformula:

-   wherein A¹ is an element selected from iodine, sulfur, selenium,    tellurium, nitrogen and phosphorus;-   when A¹ is iodine, R²⁻¹ and R³⁻¹ are not present and R¹⁻¹ is an    alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to    15 carbon atoms;-   when A¹ is sulfur, selenium or tellurium, R³⁻¹ is not present and    R¹⁻¹ and R²⁻¹ are independently an alkyl group having 1 to 15 carbon    atoms, an aryl group having 6 to 20 carbon atoms, a dialkylamino    group having 2 to 30 carbon atoms, an alkylarylamino group having 7    to 35 carbon atoms or a diarylamino group having 12 to 40 carbon    atoms and R¹⁻¹ and R²⁻¹ may be bonded to each other to constitute a    ring;-   when A¹ is nitrogen or phosphorus, R¹⁻¹, R²⁻¹ and R³⁻¹ are    independently an alkyl group having 1 to 15 carbon atoms, an aryl    group having 6 to 20 carbon atoms, a dialkylamino group having 2 to    30 carbon atoms, an alkylarylamino group having 7 to 35 carbon atoms    or a diarylamino group having 12 to 40 carbon atoms and R¹⁻¹, R²⁻¹    and R³⁻¹ may be bonded to each other to form one or more rings, or    R³⁻¹ may not be present and R¹⁻¹ and R²⁻¹ may be bonded to each    other to constitute an aromatic ring including A¹;-   the above-mentioned alkyl group, an alkyl group of the dialkylamino    group and an alkyl group of the alkylarylamino group may be    substituted with an aryl group, halogen atom, oxygen atom, nitrogen    atom, sulfur atom or silicon atom, may be branched or may constitute    a ring, and the above-mentioned aryl group, an aryl group of the    alkylarylamino group and an aryl group of the diarylamino group may    be substituted with an alkyl group, haloalkyl group, halogen atom,    alkoxyl group, aryloxy group, nitro group, amide group, cyano group,    alkanoyl group, aroyl group, alkoxycarbonyl group, aryloxycarbonyl    group or acyloxy group;-   R_(f) is a perfluoroalkyl group having 1 to 15 carbon atoms which    may be branched or may constitute a ring, or is the perfluoroalkyl    group in which a part of its fluorine atoms is substituted with    hydrogen atoms;-   X⁻ is a conjugated base of Brønsted acid, or-   a fluoroalkyl onium salt represented by the formula:

-   wherein A² and A³ are the same or different and each is an element    selected from iodine, sulfur, selenium, tellurium, nitrogen and    phosphorus;-   when A² or A³ is iodine, R⁴⁻¹, R⁵⁻¹, R⁷⁻¹ and R⁸⁻¹ are not present;-   when A² or A³ is sulfur, selenium or tellurium, R⁵⁻¹ and R⁸⁻¹ are    not present and R⁴⁻¹ and R⁷⁻¹ are independently an alkyl group    having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon    atoms, a dialkylamino group having 2 to 30 carbon atoms, an    alkylarylamino group having 7 to 35 carbon atoms or a diarylamino    group having 12 to 40 carbon atoms;-   when A² or A³ is nitrogen or phosphorus, R⁴⁻¹, R⁵⁻¹, R⁷⁻¹ and R⁸⁻¹    are independently an alkyl group having 1 to 15 carbon atoms, an    aryl group having 6 to 20 carbon atoms, a dialkylamino group having    2 to 30 carbon atoms, an alkylarylamino group having 7 to 35 carbon    atoms or a diarylamino group having 12 to 40 carbon atoms, and R⁴⁻¹    and R⁵⁻¹ or R⁷⁻¹ and R⁸⁻¹ may be bonded to each other, respectively    to constitute a ring;-   the above-mentioned alkyl group, an alkyl group of the dialkylamino    group and an alkyl group of the alkylarylamino group may be    substituted with an aryl group, halogen atom, oxygen atom, nitrogen    atom, sulfur atom or silicon atom, may be branched or may constitute    a ring, and the above-mentioned aryl group, an aryl group of the    alkylarylamino group and an aryl group of the diarylamino group may    be substituted with an alkyl group, haloalkyl group, halogen atom,    alkoxyl group, aryloxy group, nitro group, amide group, cyano group,    alkanoyl group, aroyl group, alkoxycarbonyl group, aryloxycarbonyl    group or acyloxy group;-   R⁶-1 is an alkylene group having 1 to 15 carbon atoms which may be    substituted with an aryl group, halogen atom, oxygen atom, nitrogen    atom, sulfur atom or silicon atom, may be branched or may constitute    a ring;-   R_(f) is a perfluoroalkyl group having 1 to 15 carbon atoms which    may be branched or may constitute a ring, or is the perfluoroalkyl    group in which a part of its fluorine atoms is substituted with    hydrogen atoms;-   X⁻ is a conjugated base of Brønsted acid and the like.

Examples thereof are fluoroalkyl onium salts having iodine atom as itscenter element:

Fluoroalkyl onium salt having sulfur atom as its center element:

Fluoroalkyl onium salt having selenium atom as its center element:

Fluoroalkyl onium salt having tellurium atom as its center element:

Fluoroalkyl onium salt having nitrogen atom as its center element:

Fluoroalkyl onium salt having phosphorus atom as its center element:

X⁻ in those exemplified fluoroalkyl onium salts is a conjugated base ofBrønsted acid. Non-restricted examples of the Brønsted acid arefluoroalkylsulfonic acids such as trifluoromethanesulfonic acid,tetrafluoroethanesulfonic acid, perfluorobutanesulfonic acid,perfluoropentanesulfonic acid, perfluorohexanesulfonic acid,perfluorooctanesulfonic acid and difluoromethanesulfonic acid,methanesulfonic acid, trichloromethanesulfonic acid, benzenesulfonicacid, toluenesulfonic acid, sulfuric acid, fluorosulfonic acid,chlorosulfonic acid, HBF₄, HSbF₆, HPF₆, HSbCl₅F, HSbCl₆, HAsF₆, HBCl₃F,HalCl₄ and the like. Particularly fluoroalkylsulfonic acids which arestrong acids are preferred because neither hydrogen fluoride norhydrogen chloride is generated.

Those onium salts having a fluorine-containing alkyl group are preferredbecause transparency thereof is high in a vacuum ultraviolet region andalso because of good compatibility with the fluorine-containing polymerhaving an acid-reactive group in the chemically amplifying photoresistcomposition of the present invention.

The content of photoacid generator in the photoresist composition of thepresent invention (chemically amplifying photoresist composition) ispreferably from 0.1 to 30 parts by weight, more preferably from 0.2 to20 parts by weight, most preferably from 0.5 to 10 parts by weight basedon 100 parts by weight of the fluorine-containing polymer having anacid-reactive group.

When the content of photoacid generator is less than 0.1 part by weight,sensitivity is lowered, and when the content is more than 30 parts byweight, an amount of light absorbed by the photoacid generator isincreased and light does not reach a substrate sufficiently, therebylowering resolution easily.

Also to the photoresist composition of the present invention may beadded an organic base which can act, as a base, on an acid generatedfrom the above-mentioned photoacid generator.

The purpose of adding the organic base is to prevent migration of theacid generated from the photoacid generator and to prevent a resistpattern from undergoing a dimensional change during an interval betweenthe exposure and the PEB treatment. Therefore the organic base is notlimited particularly as far as it is a compound being capable ofneutralizing the acid generated from the photoacid generator asmentioned above. The organic base is preferred because when an inorganiccompound is used as a base, a very small amount of its residue remainsafter forming a pattern and eliminating the resist and has an adverseeffect on the pattern formation. The organic base is an organic aminecompound selected from nitrogen-containing compounds.

Examples thereof are pyrimidine compounds such as pyrimidine,2-aminopyrimidine, 4-aminopyrimidine, 5-aminopyrimidine,2,4-diaminopyrimidine, 2,5-diaminopyrimidine, 4,5-diaminopyrimidine,4,6-diaminopyrimidine, 2,4,5-triaminopyrimidine,2,4,6-triaminopyrimidine, 4,5,6-triaminopyrimidine,2,4,5,6-tetraaminopyrimidine, 2-hydroxypyrimidine, 4-hydroxypyrimidine,5-hydroxypyrimidine, 2,4-dihydroxypyrimidine, 2,5-dihydroxypyrimidine,4,5-dihydroxypyrimidine, 4,6-dihydroxypyrimidine,2,4,5-trihydroxypyrimidine, 2,4,6-trihydroxypyrimidine,4,5,6-trihydroxypyrimidine, 2,4,5,6-tetrahydroxypyrimidine,2-amino-4-hydroxypyrimidine, 2-amino-5-hydroxypyrimidine,2-amino-4,5-dihydroxypyrimidine, 2-amino-4,6-dihydroxypyrimidine,4-amino-2,5-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine,2-amino-4-methylpyrimidine, 2-amino-5-methylpyrimidine,2-amino-4,5-dimethylpyrimidine, 2-amino-4,6-dimethylpyrimidine,4-amino-2,5-dimethylpyrimidine, 4-amino-2,6-dimethylpyrimidine,2-amino-4-methoxypyrimidine, 2-amino-5-methoxypyrimidine,2-amino-4,5-dimethoxypyrimidine, 2-amino-4,6-dimethoxypyrimidine,4-amino-2,5-dimethoxypyrimidine, 4-amino-2,6-dimethoxypyrimidine,2-hydroxy-4-methylpyrimidine, 2-hydroxy-5-methylpyrimidine,2-hydroxy-4,5-dimethylpyrimidine, 2-hydroxy-4,6-dimethylpyrimidine,4-hydroxy-2,5-dimethylpyrimidine, 4-hydroxy-2,6-dimethylpyrimidine,2-hydroxy-4-methoxypyrimidine, 2-hydroxy-5-methoxypyrimidine,2-hydroxy-4,5-dimethoxypyrimidine, 2-hydroxy-4,6-dimethoxypyrimidine,4-hydroxy-2,5-dimethoxypyrimidine and 4-hydroxy-2,6-dimethoxypyrimidine,pyridine compounds such as pyridine, 4-dimethylaminopyridine and2,6-dimethylpyridine, amines substituted with hydroxyalkyl group andhaving not less than 1 and not more than 4 carbon atoms such asdiethanolamine, triethanolamine, triisopropanolamine,tris(hydroxymethyl)aminomethane andbis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, aminophenols such as2-aminophenol, 3-aminophenol and 4-aminophenol and the like. Preferableorganic bases are pyrimidines, pyridines or amines having hydroxylgroup, and particularly preferred are amines having hydroxyl group.Those organic bases may be used alone or in a mixture of two or morethereof. The content of organic base in the photoresist composition ofthe present invention is preferably from 0.1 to 100% by mole, morepreferably from 1 to 50% by mole based on the content of photoacidgenerator. When the content of organic base is less than 0.1% by mole,resolution is lowered, and when the content of organic base is more than100% by mole, sensitivity tends to be lowered.

In the photoresist composition of the present invention (chemicallyamplifying photoresist composition), when a negative resist compositionis prepared using the fluorine-containing polymer, a crosslinking agentmay be used as case demands as mentioned above.

The crosslinking agent is not limited particularly and can be optionallyselected from crosslinking agents which have been usually used fornegative resists.

Examples of preferable crosslinking agent are, for instance, N-methylolmelamine, N-alkoxymethylol melamine compounds, urea compounds, epoxycompounds, isocyanate compounds and the like.

Those crosslinking agents may be used alone or in a combination of twoor more thereof. Among them, a combination of the melamine resin and theurea resin is advantageous.

The content of crosslinking agent in the photoresist (particularlynegative type) composition of the present invention is from 3 to 70parts by weight, preferably from 5 to 50 parts by weight, morepreferably from 10 to 40 parts by weight based on 100 parts by weight ofthe fluorine-containing polymer. When the content is less than 3 partsby weight, a resist pattern is difficult to be formed, and the contentof more than 70 parts by weight is not preferable because lighttransmittance is lowered, resolution is easily lowered and developingproperty is lowered.

The photoresist composition of the present invention may contain, ascase demands, various additives which have been usually used in thisfield, such as dissolution inhibitor, sensitizer, dye, adhesionbetterment material and water storage material. While the presence ofwater is necessary for generating an acid in a chemically amplifyingresist, the acid can be generated effectively in the presence of a smallamount of water storage material such as polypropylene glycol.

When those additives are used, a total amount thereof is up to about 20%by weight based on the weight of the whole solids in the composition.

In the photoresist composition of the present invention (chemicallyamplifying photoresist composition), the solvent (C) is one which iscapable of dissolving the fluorine-containing polymer, the photoacidgenerator (B) and the above-exemplified various additives. The solventis not limited particularly as far as good coatability (surfacesmoothness, uniformity of coating thickness, etc.) can be obtained.

Examples of the preferable solvent (C) are, for instance, cellosolvesolvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolveacetate and ethyl cellosolve acetate, ester solvents such as diethyloxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate,butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, methyllactate, ethyl lactate, methyl 3-methoxypropionate, ethyl3-methoxypropionate, methyl 2-hydroxyisobutyrate and ethyl2-hydroxyisobutyrate, propylene glycol solvents such as propylene glycolmonomethyl ether, propylene glycol monoethyl ether, propylene glycolmonobutyl ether, propylene glycol monomethyl ether acetate, propyleneglycol monoethyl ether acetate, propylene glycol monobutyl ether acetateand dipropylene glycol dimethyl ether, ketone solvents such as2-hexanone, cyclohexanone, methyl amino ketone and 2-heptanone, aromatichydrocarbons such as toluene, xylene, chlorobenzene and chlorotoluene, asolvent mixture of two or more thereof and the like.

Also in order to enhance solubility of the fluorine-containing polymer,a fluorine-containing solvent may be used as case demands.

Examples thereof are, for instance, CH₃CCl₂F (HCFC-141b), a mixture ofCF₃CF₂CHCl₂ and CClF₂CF₂CHClF (HCFC-225), perfluorohexane,perfluoro(2-butyltetrahydrofuran), methoxy-nonafluorobutane,1,3-bistrifluoromethylbenzene, and in addition, fluorine-containingalcohols such as:

H(CF₂CF₂

_(n)CH₂OH (n: an integer of from 1 to 3)

F(CF₂

_(n)CH₂OH (n: an integer of from 1 to 5) and

(CF₃

₂CHOH,

benzotrifluoride, perfluorobenzene, perfluoro(tributylamine),ClCF₂CFClCF₂CFCl₂ and the like.

Those fluorine-containing solvents may be used alone, in a mixture oftwo or more thereof or in a mixture of one or more of thefluorine-containing solvents and non-fluorine-containing solvents.

The amount of the solvent (C) is selected depending on kind of solids tobe dissolved, kind of a substrate to be coated, an intended coatingthickness, etc. From the viewpoint of easiness of coating, it ispreferable that the solvent is used in such an amount that theconcentration of the whole solids of the resist composition becomes from0.5 to 70% by weight, preferably from 1 to 50% by weight, particularlypreferably from 5 to 30% by weight.

The photoresist composition of the present invention (chemicallyamplifying resist composition) is subjected to resist pattern formationaccording to conventional photoresist technology. In order to form apattern properly, first, a solution of the resist composition is appliedon a substrate such as a silicon wafer by a spinner or the like, and isdried to form a photosensitive layer. A pattern is drawn by irradiatingthe layer with ultraviolet ray, deep-UV, excimer laser or X-ray by areduction projection exposure system, etc. through a proper mask patternor the pattern is drawn with an electron beam, and then heating follows.The layer is then subjected to developing treatment with a developingsolution, for example, an aqueous alkaline solution such as an aqueoussolution of 1 to 10% by weight of tetramethylammonium hydroxide. Thus animage faithful to the mask pattern can be obtained by theabove-mentioned pattern forming method.

It was found that by using the photoresist composition of the presentinvention (chemically amplifying resist composition), a resist film(photosensitive layer) having a high transparency even in a vacuumultraviolet region could be formed. Therefore the resist composition ofthe present invention can be preferably used particularly for aphotolithography process using a F₂ laser (wavelength of 157 nm) whichis under development aiming at a technology node of 0.1 μm.

The tenth of the present invention relates to a fluorine-containingcyclopentene having OH group which is represented by the formula (70):

wherein Rf⁷⁰ is a perfluoroalkyl group having 1 to 20 carbon atoms; X⁷⁰is fluorine atom or a perfluoroalkyl group having 1 to 20 carbon atoms;X⁷¹ is hydrogen atom, fluorine atom, a hydrocarbon group having 1 to 20carbon atoms or a perfluoroalkyl group having 1 to 20 carbon atoms; X⁷²is hydrogen atom, fluorine atom, OH group, a hydrocarbon group having 1to 20 carbon atoms or a perfluoroalkyl group having 1 to 20 carbonatoms; X⁷³ is hydrogen atom, fluorine atom, a hydrocarbon group having 1to 20 carbon atoms or a perfluoroalkyl group having 1 to 20 carbonatoms; when X⁷² is OH group, X⁷³ is not fluorine atom, and thefluorine-containing cyclopentene having OH group can impart recurringunits of monocyclic structure to the polymer.

This novel monocyclic monomer is high in copolymerizability with afluoroolefin as mentioned above, and therefore, OH group can beintroduced easily to the polymer and solubility in a developing solutionand other functions (for example, transparency in a vacuum ultravioletregion) can be imparted to the polymer. Also since a monocyclicstructural unit can be introduced in the polymer trunk chain, a glasstransition temperature can be increased and therefore the polymer ispreferred from the viewpoint of dry etching resistance.

In the above-mentioned formula (70), it is particularly preferable thatboth of X⁷⁰ and X⁷¹ are fluorine atoms or perfluoroalkyl groups having 1to 20 carbon atoms and further it is preferable that X⁷² is OH group andX⁷³ is a perfluoroalkyl group having 1 to 20 carbon atoms, sinceexcellent solubility in a developing solution and transparency can beimparted to the polymer.

Examples of the novel fluorine-containing cyclopentene having OH groupof the present invention are, for instance,

and the like as mentioned above.

Those monomers which are novel cyclopentene derivatives can besynthesized by the processes of the preparation schemes (1) to (4)mentioned supra.

Those monomers can be polymerized alone using a radical polymerizationinitiator or a cation polymerization initiator, and further can besubjected to radical polymerization with the above-mentioned variousfluoroolefins (monomers providing the structural unit M1), acrylicmonomers and α-olefins, thereby being capable of imparting hydrophilicproperty, solubility in a developing solution, transparency and othervarious functions to the polymer.

EXAMPLE

The present invention is then explained by means of examples but is notlimited to them.

In the following Examples, equipment and measuring conditions used forevaluation of physical properties are as follows.

-   (1) NMR: NMR analyzer is AC-300 available from BRUKER CO., LTD.    Measuring conditions of ¹H-NMR: 300 MHz (tetramethylsilane=0 ppm)    Measuring conditions of ¹⁹F-NMR: 280 MHz (trichlorofluoromethane=0    ppm) Measuring conditions of ¹³C-NMR: 75 MHz (tetramethylsilane=0    ppm)-   (2) IR analysis: Measuring is carried out at room temperature with a    Fourier-transform infrared spectrophotometer 1760X available from    Perkin Elmer Co., Ltd.-   (3) GPC: A number average molecular weight is calculated from data    measured by gel permeation chromatography (GPC) by using GPC    HLC-8020 available from Toso Kabushiki Kaisha and columns available    from Shodex Co., Ltd. (one GPC KF-801, one GPC KF-802 and two GPC    KF-806M were connected in series) and flowing tetrahydrofuran (THF)    as a solvent at a flowing rate of 1 ml/minute.

Example 1 Synthesis of Copolymer Comprising Cyclopentene andTetrafluoroethylene

A 100 ml autoclave was charged with 3.4 g of cyclopentene:

40 ml of HCFC-141b and 0.3 g ofbis(4-tert-butylcyclohexyl)peroxydicarbonate (TCP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling withdry ice/methanol solution. Then 10.0 g of tetrafluoroethylene (TFE) wasintroduced through a valve, followed by shaking for reaction at 40° C.for 18 hours. With the advance of the reaction, a gauge pressure wasdecreased from 0.78 MPaG (8.0 kgf/cm²G) before the reaction to 0.75 MPaG(7.7 kgf/cm²G).

After releasing the un-reacted monomer, the polymerization solution wasremoved, followed by re-precipitation with hexane to separate acopolymer. Until a constant weight was reached, vacuum drying wascontinued and 1.5 g of a copolymer was obtained. As a result of ¹H-NMRand ¹⁹F-NMR analyses, the copolymer was one represented by the followingformula.

The copolymer was one comprising TFE/cyclopentene in a percent by moleratio of 50/50 according to an elementary analysis. According to GPCanalysis, a number average molecular weight of the copolymer was 5,700.

Example 2 Synthesis of Copolymer Comprising 2,3-dihydrofuran andTetrafluoroethylene

Reaction was carried out in the same manner as in Example 1 except that3.5 g of 2,3-dihydrofuran:

was used instead of cyclopentene.

With the advance of the reaction, a gauge pressure was decreased from0.78 MPaG (8.0 kgf/cm²G) before the reaction to 0.75 MPaG (7.7kgf/cm²G).

After releasing the un-reacted monomer, a polymer was separated in thesame manner as in Example 1 and 2.1 g of a copolymer was obtained. As aresult of ¹H-NMR and ¹⁹F-NMR analyses, the copolymer was one representedby the following formula.

The copolymer was one comprising TFE/2,3-dihydrofuran in a percent bymole ratio of 50/50 according to an elementary analysis. According toGPC analysis, a number average molecular weight of the copolymer was17,000.

Example 3 Synthesis of Copolymer Comprising Cyclooctene andTetrafluoroethylene

A 100 ml autoclave was charged with 2.8 g of cyclooctene:

40 ml of HCFC-141b and 0.4 g ofbis(4-tert-butylcyclohexyl)peroxydicarbonate (TCP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling withdry ice/methanol solution. Then 10.0 g of tetrafluoroethylene (TFE) wasintroduced through a valve, followed by shaking for reaction at 40° C.for 18 hours. With the advance of the reaction, a gauge pressure wasdecreased from 0.88 MPaG (9.0 kgf/cm²G) before the reaction to 0.84 MPaG(8.6 kgf/cm²G).

After releasing the un-reacted monomer, the polymerization solution wasremoved, followed by re-precipitation with methanol to separate acopolymer. Until a constant weight was reached, vacuum drying wascontinued and 2.7 g of a copolymer was obtained. As a result of ¹H-NMRanalysis, the copolymer was one represented by the following formula.

The copolymer was one comprising TFE/cyclooctene in a percent by moleratio of 52/48 according to an elementary analysis. According to GPCanalysis, a number average molecular weight of the copolymer was 9,900.

Example 4 Synthesis of Copolymer Comprising 3,3′-dimethylcyclopropeneand Tetrafluoroethylene

A 300 ml autoclave was charged with 4.0 g of 3,3′-dimethylcyclopropene:

140 ml of HCFC-141b and 0.8 g ofbis(4-tert-butylcyclohexyl)peroxydicarbonate (TCP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling withdry ice/methanol solution. Then 23.5 g of tetrafluoroethylene (TFE) wasintroduced through a valve, followed by shaking for reaction at 40° C.for 18 hours. With the advance of the reaction, a gauge pressure wasdecreased from 0.80 MPaG (8.2 kgf/cm²G) before the reaction to 0.65 MPaG(6.6 kgf/cm²G).

After releasing the un-reacted monomer, the polymerization solution wasremoved, followed by re-precipitation with methanol to separate acopolymer. Until a constant weight was reached, vacuum drying wascontinued and 1.7 g of a copolymer was obtained. As a result of ¹H-NMRanalysis, the copolymer was one represented by the following formula.

The copolymer was one comprising TFE/3,3′-dimethylcyclopropene in apercent by mole ratio of 61/39 according to an elementary analysis.

Example 5 Synthesis of Copolymer Comprising Dicyclopentene andTetrafluoroethylene

A 100 ml autoclave was charged with 3.4 g of dicyclopentene:

40 ml of HCFC-141b and 0.4 g ofbis(4-tert-butylcyclohexyl)peroxydicarbonate (TCP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling withdry ice/methanol solution. Then 10.0 g of tetrafluoroethylene (TFE) wasintroduced through a valve, followed by shaking for reaction at 40° C.for 18 hours. With the advance of the reaction, a gauge pressure wasdecreased from 0.90 MPaG (9.2 kgf/cm²G) before the reaction to 0.88 MPaG(9.0 kgf/cm²G).

After releasing the un-reacted monomer, the polymerization solution wasremoved, followed by re-precipitation with methanol to separate acopolymer. Until a constant weight was reached, vacuum drying wascontinued and 1.0 g of a copolymer was obtained.

As a result of ¹H-NMR analysis, the copolymer was one having thefollowing structure. Also according to IR analysis, an absorption ofcarbon-carbon double bond was recognized.

The copolymer was one comprising TFE/dicyclopentene in a percent by moleratio of 51/49 according to an elementary analysis. Also according to IRanalysis, an absorption of carbon-carbon double bond was recognized.According to GPC analysis, a number average molecular weight of thecopolymer was 3,800.

Example 6 Synthesis of Copolymer Comprising 2,3-dihydrofuran,tetrafluoroethylene and tert-butyl-αfluoroacrylate

A 500 ml autoclave was charged with 7.0 g of 2,3-dihydrofuran, 5.8 g oftert-butyl-αfluoroacrylate, 40 ml of HCFC-141b and 0.8 g ofbis(4-tert-butylcyclohexyl)peroxydicarbonate (TCP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling withdry ice/methanol solution. Then 40.0 g of tetrafluoroethylene (TFE) wasintroduced through a valve, followed by shaking for reaction at 40° C.for 18 hours. With the advance of the reaction, a gauge pressure wasdecreased from 0.88 MPaG (9.0 kgf/cm²G) before the reaction to 0.86 MPaG(8.8 kgf/cm²G).

After releasing the un-reacted monomer, the polymerization solution wasremoved, followed by re-precipitation with hexane to separate acopolymer. Until a constant weight was reached, vacuum drying wascontinued and 11.2 g of a copolymer was obtained.

As a result of ¹H-NMR and ¹⁹F-NMR analyses, the copolymer was onecomprising TFE/2,3-dihydrofuran/tert-butyl-αfluoroacrylate in a percentby mole ratio of 23/33/44. According to GPC analysis, a number averagemolecular weight of the copolymer was 18,000.

Example 7 Synthesis of Copolymer Comprising cyclopentene,tetrafluoroethylene and tert-butyl-αfluoroacrylate

A 100 ml autoclave was charged with 3.4 g of cyclopentene, 1.5 g oftert-butyl-αfluoroacrylate, 40 ml of HCFC-141b and 0.3 g ofbis(4-tert-butylcyclohexyl)peroxydicarbonate (TCP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling withdry ice/methanol solution. Then 10.0 g of tetrafluoroethylene (TFE) wasintroduced through a valve, followed by shaking for reaction at 40° C.for 18 hours. With the advance of the reaction, a gauge pressure wasdecreased from 0.78 MPaG (8.0 kgf/cm²G) before the reaction to 0.77 MPaG(7.9 kgf/cm²G).

After releasing the un-reacted monomer, the polymerization solution wasremoved, followed by re-precipitation with hexane to separate acopolymer. Until a constant weight was reached, vacuum drying wascontinued and 2.2 g of a copolymer was obtained.

As a result of ¹H-NMR and ¹⁹F-NMR analyses, the copolymer was onecomprising TFE/cyclopentene/tert-butyl-αfluoroacrylate in a percent bymole ratio of 15.1/39.3/45.6. According to GPC analysis, a numberaverage molecular weight of the copolymer was 12,000.

Example 8 Synthesis of Copolymer Comprising cyclopentene,tetrafluoroethylene and tert-butyl-αfluoroacrylate

Reaction was carried out in the same manner as in Example 7 except that1.7 g of cyclopentene and 1.5 g of tert-butyl-αfluoroacrylate were used.With the advance of the reaction, a gauge pressure was decreased from0.78 MPaG (8.0 kgf/cm²G) before the reaction to 0.74 MPaG (7.6kgf/cm²G).

After releasing the un-reacted monomer, a polymer was isolated in thesame manner as in Example 7 and 1.7 g of a copolymer was obtained.

As a result of ¹H-NMR and ¹⁹F-NMR analyses, the copolymer was onecomprising TFE/cyclopentene/tert-butyl-αfluoroacrylate in a percent bymole ratio of 26.7/34.1/39.2. According to GPC analysis, a numberaverage molecular weight of the copolymer was 14,000.

Example 9 Synthesis of Copolymer Comprising cyclopentene,tetrafluoroethylene and tert-butyl-αfluoroacrylate

Reaction was carried out in the same manner as in Example 7 except that3.4 g of cyclopentene and 4.5 g of tert-butyl-αfluoroacrylate were used.With the advance of the reaction, a gauge pressure was decreased from0.78 MPaG (8.0 kgf/cm²G) before the reaction to 0.75 MPaG (7.7kgf/cm²G).

After releasing the un-reacted monomer, a polymer was isolated in thesame manner as in Example 7 and 3.5 g of a copolymer was obtained.

As a result of ¹H-NMR and ¹⁹F-NMR analyses, the copolymer was onecomprising TFE/cyclopentene/tert-butyl-αfluoroacrylate in a percent bymole ratio of 6.6/51.9/41.5. According to GPC analysis, a number averagemolecular weight of the copolymer was 21,000.

Example 10 Synthesis of Copolymer Comprising2-cyclopentene-1-tert-butylacetate and tetrafluoroethylene

A 100 ml autoclave was charged with 4.6 g of2-cyclopentene-1-tert-butylacetate:

40 ml of HCFC-141b and 0.5 g ofbis(4-tert-butylcyclohexyl)peroxydicarbonate (TCP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling withdry ice/methanol solution. Then 10.0 g of tetrafluoroethylene (TFE) wasintroduced through a valve, followed by shaking for reaction at 40° C.for 18 hours. With the advance of the reaction, a gauge pressure wasdecreased from 0.98 MPaG (10.0 kgf/cm²G) before the reaction to 0.96MPaG (9.8 kgf/cm²G).

After releasing the un-reacted monomer, the polymerization solution wasremoved, followed by re-precipitation with hexane to separate acopolymer. Until a constant weight was reached, vacuum drying wascontinued and 1.0 g of a copolymer was obtained. As a result of ¹H-NMRanalysis, the copolymer was one represented by the following formula.

The copolymer was one comprising TFE/2-cyclopentene-1-tert-butylacetatein a percent by mole ratio of 50/50 according to an elementary analysis.According to GPC analysis, a number average molecular weight of thecopolymer was 1,800.

Example 11 Synthesis of Copolymer Comprising diallylmalonate ethyl esterand tetrafluoroethylene

A 100 ml autoclave was charged with 9.6 g of diallylmalonate ethylester:

40 ml of HCFC-225 and 0.18 g ofbis(4-tert-butylcyclohexyl)peroxydicarbonate (TCP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling withdry ice/methanol solution. Then 8.0 g of tetrafluoroethylene (TFE) wasintroduced through a valve, followed by shaking for reaction at 40° C.for 20 hours. With the advance of the reaction, a gauge pressure wasdecreased from 0.78 MPaG (8.0 kgf/cm²G) before the reaction to 0.64 MPaG(6.5 kgf/cm²G).

After releasing the un-reacted monomer, the polymerization solution wasremoved, followed by concentration and re-precipitation with hexane toseparate a copolymer. Until a constant weight was reached, vacuum dryingwas continued and 12.0 g of a copolymer was obtained.

As a result of an elementary analysis, the copolymer was one comprisingTFE/diallylmalonate ethyl ester in a percent by mole ratio of 52/48.According to GPC analysis, a number average molecular weight of thecopolymer was 11,000.

As a result of IR and ¹H-NMR analyses, disappearing of a peak of C═Cdouble bond which could be recognized in a diallylmalonate ethyl estermonomer was confirmed. Also according to ¹³C-NMR and DEPT analyses, itwas confirmed that the diallylmalonate ethyl ester unit in the copolymerwas a 5-membered ring represented by the following formula.

This copolymer was dissolved uniformly in the solvents such as acetone,THF, DMF and HFC-225.

Example 12 Synthesis of cyclopentene Having —C(CF₃)₂OH Group

A 500 ml four-necked glass flask equipped with a blowing tube wascharged with 100 g of cyclopentadiene, followed by stirring in nitrogengas atmosphere while cooling in dry ice/acetone bath. HCl gas was slowlyintroduced at a solution temperature of not more than 0° C. through agas feeding tube and sometimes the flask was separated to measure theweight thereof. HCl gas was introduced up to 90% of theoretical amountto synthesize 3-chlorocyclopentene which was not isolated and used forthe following reaction.

Magnesium was put in an amount of 24 g into a 1-liter four-necked glassflask equipped with a blowing tube, dry ice condenser and droppingfunnel and was dried by heating in vacuo. Thereto was added 200 ml ofTHF, followed by cooling in ice bath. A solution obtained by mixing 31 gof previously prepared 3-chlorocyclopentene to 150 ml of THF was slowlyadded dropwise through the dropping funnel in a state of the solutiontemperature being 10° to 15° C. After completion of the addition,hexafluoroacetone was introduced slowly through the gas feeding tube sothat the solution temperature did not exceed 20° C. Hexafluoroacetonewas introduced until generation of heat was not recognized. Aftercompletion of the introduction of hexafluoroacetone, stirring wasfurther continued at room temperature for three hours. The reactionmixture was put in 500 ml of 1N hydrochloric acid, followed byseparating an organic layer, washing with water, drying and distillingafter concentration. As a result, 56.0 g of fluorine-containing alcoholrepresented by the formula:

having a boiling point of from 62° to 64° C./45 mmHg was obtained. Themonomer obtained above was determined by ¹⁹F-NMR, ¹H-NMR, ¹³C-NMR and IRanalyses.

Example 13 Synthesis of Copolymer Comprising tetrafluoroethylene andcyclopentene Having —C(CF₃)₂OH Group)

A 100 ml autoclave was charged with 5.5 g of the cyclopentene having—C(CF₃)₂OH group obtained in Example 12, 40 ml of HCFC-141b and 0.7 g ofbis(4-tert-butylcyclohexyl)peroxydicarbonate (TCP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling withdry ice/methanol solution. Then 10.0 g of tetrafluoroethylene (TFE) wasintroduced through a valve, followed by shaking for reaction at 40° C.for 18 hours. With the advance of the reaction, a gauge pressure wasdecreased from 0.88 MPaG (9.0 kgf/cm²G) before the reaction to 0.85 MPaG(8.7 kgf/cm²G).

After releasing the un-reacted monomer, the polymerization solution wasremoved, followed by re-precipitation with hexane to separate acopolymer. Until a constant weight was reached, vacuum drying wascontinued and 1.2 g of a copolymer having a structure represented by thefollowing formula was obtained.

As a result of ¹H-NMR and ¹⁹F-NMR analyses, the copolymer was onecomprising TFE/cyclopentene having —C(CF₃)₂OH group in a percent by moleratio of 50/50.

Example 14 Measurement of Transparency at a Wavelength of 157 nm

(1) Preparation of Coating Composition

The fluorine-containing polymers prepared in Examples 1 to 3, 6 to 10and 13 were dissolved in butyl acetate so that the concentration thereofbecame 3%, respectively. Thus coating compositions were prepared.

(2) Coating

(i) Coating on a Substrate (MgF₂) for Measuring Transparency

Each coating composition was applied on a MgF₂ substrate at roomtemperature with a spin coater under the condition of 1,000 rpm. Afterthe coating, the coating composition was baked at 100° C. for 15 minutesto form transparent coating films.

(ii) Measurement of Coating Thickness

Coating films were formed by applying the respective coatingcompositions under the same conditions as above except that a siliconwafer was used instead of the MgF₂ substrate.

The coating thickness was measured with a AFM device (SPI3800 availablefrom SEIKO DENSHI KABUSHIKI KAISHA). The results are shown in Table 1.

(3) Measurement of Transparency in Vacuum Ultraviolet Region

(i) Measuring Device

-   -   Setani-Namioka type spectrometer (BL-7B available from HIGH        ENERGY KENKYU KIKO)    -   Slit: 7/8-7/8    -   Detector: PMT    -   Grating (GII: Blaze wavelength 160 nm, 1,200 gratings/mm)

For an optical system, refer to Rev. Sic. Instrum., 60(7), 1917 (1989)by H. Namba, et al.

(ii) Measurement of Transmitting Spectrum

A transmitting spectrum at a wavelength of 200 to 100 nm in a coatingfilm formed by applying each coating composition on the MgF₂ substrateby the method of (2)(i) was measured using the above-mentioned device.

A molecular absorption coefficient was calculated from the transmittanceat 157 nm and the coating thickness and is shown in Table 1.

Example 15 Evaluation of Dry Etching Resistance

10% butyl acetate solutions of fluorine-containing polymers prepared inExamples 1 to 3, 6 to 10 and 13 were prepared and coated on a Sisubstrate with a spin coater so that the coating thickness became 200nm. After the coating film was pre-baked at 120° C. for 2 minutes, thecoating thickness was measured with an interference coating thicknessmeter. Then the coated substrate was put in a chamber of ICP(inductively-coupled plasma) etching equipment to carry out etching. Apressure of etching gas (Ar/N₂/C₄F₈ mixed gas) was 1.33 Pa (10 mTorr).Plasma etching was carried out at 13.56 MHz and 900 W for an upperelectrode and at 400 kHz and 100 W for a lower electrode. An etchingtime was 60 seconds.

The coating thickness after the etching was measured with aninterference coating thickness meter and an etching rate was calculated.For comparison, an etching rate was obtained similarly using a resist(TArF-6a-63 available from Tokyo Oka Kabushiki Kaisha) used forlithography for ArF laser. The etching rate is represented in comparisonwith the rate obtained for comparison. Namely, each etching rate isshown by a ratio to the etching rate of comparative polymer (theabove-mentioned resist for ArF laser) provided that the latter etchingrate is 1. The results are shown in Table 1.

Example 16 Evaluation of Solubility in Developing Solution

(1) Deprotection Reaction of Protective Group

Each protective group contained in the fluorine-containing polymers ofExamples 6 to 10 and 13 was subjected to deprotection by reacting thefluorine-containing polymers with trifluoroacetic acid by usingdichloromethane solvent.

It was confirmed by ¹H-NMR and IR analyses that 85% or more ofprotective groups were deprotected and converted to COOH group.

(2) Coating

10% butyl acetate solutions of fluorine-containing polymers prepared inExamples 6 to 10 and 13 and deprotected fluorine-containing polymersobtained above were prepared and coated on a Si substrate with a spincoater so that a coating thickness became 200 nm, followed by drying.

(3) Determination of Solubility

The Si substrate after the drying was dipped in a 2.38% aqueous solutionof tetramethylammonium hydroxide for 60 seconds. Then the substrate wasremoved and dried at room temperature, and whether or not there was aremaining film was checked with naked eyes.

When there remain no film, solubility is assumed to be ◯. The resultsare shown in Table 1

Example 17

(1) Preparation of Coating Composition

The fluorine-containing polymers prepared in Examples 6 to 10 and 13 anda photoacid generator (B) in an amount of 5% by weight based on thepolymer were dissolved in butyl acetate as the solvent (C) and aconcentration of the polymer was diluted to 5% by weight.

As the photoacid generator,S-(trifluoromethyl)-dibenzothiopheniumtrifluoromethane sulfonate:

was used.(2) Coating

Coating compositions were coated on a Si substrate with a spin coater sothat a coating thickness became 200 nm, followed by drying.

(3) Measurement of Transparency in Vacuum Ultraviolet Region

Measurement was made in the same manner as in Example 14. A molecularabsorption coefficient at 157 nm is shown in Table 1.

TABLE 1 Ex. 16 Ex. 14 Solubility in Ex. 17 Absorption developingAbsorption Fluorine- coefficient Ex. 15 solution coefficient containingat 157 nm Etching rate Before After at 157 nm polymer (μm⁻¹) (to ArFresist) deprotection deprotection (μm⁻¹) Ex. 1 0.9 0.8 — — — Ex. 2 1.00.9 — — — Ex. 3 1.1 0.9 — — — Ex. 6 3.5 1.05 X ◯ 3.7 Ex. 7 3.6 1.2 X ◯3.9 Ex. 8 3.7 1.1 X ◯ 3.9 Ex. 9 4.1 1.5 X ◯ 4.4 Ex. 10 3.2 0.9 X ◯ 3.4Ex. 13 0.7 1.0 ◯ — 1.0

Example 18 Synthesis of Fluorine-containing Cyclopentene DerivativeHaving OH Group

(1) Synthesis of CF₃COCF₂COCF₃

A 500 ml four-necked glass flask was charged with 31.2 g ofCF₃COCH₂COCF₃ and 250 ml of acetonitrile, followed by replacement withnitrogen at 0° C. The mixture was cooled to −10° C. and thereto wasintroduced 10% by volume of F₂/N₂ (600 mmol as F₂, four times the molarquantity) over five hours. As a result, the solution temperature wasincreased to a temperature near 5° C. After the introduction of fluorinegas, nitrogen gas was flowed at 0° C. for 30 minutes to purge fluorinegas. Then a solution prepared by dissolving 52 g of BF₃.NEt₃ in 20 ml ofacetonitrile was added dropwise at 0° C. After completion of theaddition, stirring was further carried out at room temperature for 15hours and the flask was heated to 50° C. in an oil bath, followed bydistilling in nitrogen gas atmosphere to obtain 26.4 g of CF₃COCF₂COCF₃(boiling point: 34° to 35° C.). According to ¹⁹F-NMR, ¹H-NMR, ¹³C-NMRand IR analyses, the obtained product was determined as CF₃COCF₂COCF₃.

(2) Synthesis of Diene.diol Derivative with CH₂═CHMgBr and C₂H₅OCH₂Cl

The inside of a 500 ml four-necked glass flask was replaced withnitrogen and 10.5 g of CF₃COCF₂COCF₃ and 50 ml of THF were introducedthereto, followed by cooling the flask in an ice bath. Then 129 ml of 1NTHF solution of CH₂═CHMgBr was slowly added thereto dropwise so that thesolution temperature did not exceed 10° C. After completion of theaddition, the solution temperature was increased to room temperatureover one hour and the flask was again cooled to 0° C. in an ice bath.Then 21.3 g of C₂H₅OCH₂Cl and 81 ml of DMF were slowly added theretodropwise through a dropping funnel so that the solution temperature didnot exceed 10° C. After stirring at room temperature for 24 hours, thereaction solution was poured into 1 liter of water to separate anorganic layer. An aqueous layer was extracted with 200 ml of hexane, andwashed together with the organic layer using 200 ml of 1N HCl two timesand 200 ml of saturated brine once, followed by drying with potassiumcarbonate, concentrating with an evaporator and separating andcollecting a concentrated residue with a silica gel column (a developingsolvent was ethyl acetate:hexane=1:15, Rf value was 0.2). The obtainedfraction was concentrated with an evaporator and 15.2 g of diene.diolderivative represented by the formula:

was obtained. The above-mentioned structure was determined according to¹⁹F-NMR, ¹H-NMR, ¹³C-NMR and IR analyses.(3) Synthesis of Cyclopentene.Diol Derivative by Metathesis Ring-ClosingReaction

In 50-liter two-necked flask was put 0.8 g of PhCH═RuCl₂ (PCy₃)₂ (Cyrepresents cyclohexyl), followed by replacement with nitrogen. Thenthereto were added 2 liter of CH₂Cl₂ subjected to drying and deaerationand 8.32 g of diene•diol derivative prepared above. Stirring wascontinued at room temperature for 24 hours, followed by concentratingand separating and collecting with a silica gel column (a developingsolvent was ethyl acetate:hexane=1:20, Rf value was 0.25). The obtainedfraction was concentrated with an evaporator and 6.21 g ofcyclopentene.diol derivative represented by the formula:

was obtained. The above-mentioned structure was determined according to¹⁹F-NMR, ¹H-NMR, ¹³C-NMR and IR analyses.(4) Deprotection of Cyclopentene.Diol Derivative

In a four-necked flask equipped with a refluxing tube were put 15 g ofcyclopentene•diol derivative obtained above, 40 ml of dichloromethane, 4g of trifluoroacetic acid and 1 g of water, followed by refluxing at 40°C. for 12 hours. The separation of solution and distillation werecarried out and 8.5 g of fluorine-containing cyclopentene.diolrepresented by the formula:

was obtained. The above-mentioned structure was determined according to¹⁹F-NMR, ¹H-NMR, ¹³C-NMR and IR analyses.

Experimental Example 1 Relation Between pKa Value and ΔH ofFluorine-Containing Ethylenic Monomer Having OH Group

(1) Calculation of ΔH of Fluorine-Containing Ethylenic Monomers HavingOH Group

With respect to various fluorine-containing ethylenic monomers having OHgroup shown in Table 2, calculation of molecular orbital was carried outby the above-mentioned MOPAC97, AM1 method to calculate a producedenthalpy H(M-OH) before acid dissociation and a produced enthalpyH(M-O⁻) after acid dissociation. With respect to the monomers having along chain, calculation of molecular orbital was carried out using themodel structures shown in Table 2. Then provided that a producedenthalpy of hydrogen ion is a constant of 200 kJ/mol, each producedenthalpy was substituted in the following Equation 3:ΔH═H(M-O⁻)+200−H(M-OH)  (Equation 3)to obtain ΔH (kJ/mol). The results are shown in Table 2.(2) (Measurement of pKa Value of Various Fluorine-containing CompoundsHaving OH Group)Measurement of pKa Value of Cyclopentene Derivative Having —C(CF₃)₂OHGroup

In a water/acetone mixture (10/15 ml) solution was put 0.4045 g of theabove-mentioned cyclopentene derivative, followed by stirring at roomtemperature. After it was confirmed that the solution becamehomogeneous, titration was carried out with about 0.2 mol/liter NaOHsolution. A titration curve was obtained by adding a NaOH solutiondropwise in increments of 0.15 ml and recording a pH value at everyaddition. An equivalence point was determined by an inflection point(maximum differential value of titration curve=dpH/dml) of the titrationcurve. In this case, the equivalence point was 8.0 ml. A pH value at 4.0ml which was a half of the equivalence point was read from the titrationcurve and was found to be 11.12. From a titration curve of water/acetonesolution and aqueous solution which had been measured previously as ablank solution, a difference in a pH value derived from an electricpotential difference between the solutions at titration of 4.0 ml was1.50. Therefore from 11.12−1.50=9.62, a pKa value of this norbornenederivative was determined as 9.62.

In the case of titration of 0.8104 g of cyclopentene derivative by thesame procedures as above, an equivalence point was 16.4 ml and a half ofequivalence point was 8.4 ml. A pH value at a half of the equivalencepoint was 11.14. A difference in a pH value between the both solutionsat 8.4 ml was 1.19, and from 11.14−1.19=9.95, a pKa value of thecyclopentene derivative was determined as 9.95.

In the case of titration of 0.9812 g of cyclopentene derivative by thesame procedures as above, an equivalence point thereof was 18.95 ml anda half of equivalence point was 9.48 ml. A pH value at this time was11.03. A difference in a pH value between the both solutions at 9.48 mlwas 1.17, and from 11.03−1.17=9.86, a pKa value of the cyclopentenederivative was determined as 9.86.

From those experiments carried out three times, a pKa value of thecyclopentene derivative was determined as 9.8.

With respect to the various fluorine-containing compounds having OHgroup shown in Table 2, a pKa value was measured by the same proceduresas above. The results are shown in Table 2.

(3) Relation Between ΔH and Actually Measured pKa

With respect to the various fluorine-containing compounds having OHgroup shown in Table 2, FIG. 1 is a graph in which calculated AH andactually measured pKa are plotted in an abscissa and an ordinate,respectively. As shown in FIG. 1, it was found that a good proportionalrelation is exhibited.

From the graph, an equation:(pKa)=0.0442·ΔH+6.8613  (Equation 4)(R²=0.9224) was obtained.

TABLE 2 Fluorine-containing compound (1) (2) having OH group Modelstructure ΔH pKa

60.5 9.8

59.5 10.2

40.4 9.0

29.9 8.3

116.3 11.5 CH₂═CHCH₂C(CF₃)₂OH CH₂═CHCH₂C(CF₃)₂OH 74.2 9.6CF₂═CF—C(CF₃)₂OH CH₂═CHCH₂C(CF₃)₂OH 13.2 7.1 CF₃CH(CF₃)—OHCH₂═CHCH₂C(CF₃)₂OH 50.4 9.3 CH₂═CF—C(CF₃)₂OH CH₂═CHCH₂C(CF₃)₂OH 38.7 8.0

122.3 12.6

The novel fluorine-containing polymer of the present invention possessesdry etching resistance higher than that of polymers prepared usingnorbornene and transparency thereof even in a vacuum ultraviolet regionis excellent as compared with polymers prepared using norbornene.

Also the copolymer obtained by copolymerizing a fluoroolefin with thenovel unsaturated compound having a monocyclic structure of the presentinvention which has an acid-reactive functional group directly bonded toa ring and partly contains fluorine possesses an excellent dry etchingresistance and high transparency when used for a resist.

1. A fluorine-containing unsaturated cyclic compound represented by theformula (1)(a):

wherein Z³ are the same or different and each is —Rf³-Z⁴, in which Z⁴ isat least one functional group selected from the group consisting of OHgroup, COOH group, a derivative of carboxylic acid group and afunctional group protected by a protective group which can convert thefunctional group to OH group by reaction with an acid; Rf³ is afluorine-containing alkylene group which has 1 to 30 carbon atoms andmay have ether bond; n11 is an integer of from 1 to
 4. 2. Thefluorine-containing unsaturated cyclic compound of claim 1, wherein inthe formula (1)(a), Z³ is represented by the formula:—Rf⁴—COOR¹⁴ wherein Rf⁴ is a perfluoroalkylene group which has 1 to 10carbon atoms and may have ether bond; R⁴ is hydrogen atom or an alkylgroup having 1 to 10 carbon atoms.
 3. The fluorine-containingunsaturated cyclic compound of claim 1, wherein in the formula (1)(a),Z³ is represented by the formula:

wherein R¹⁵ is an alkylene group which has 1 to 5 carbon atoms and mayhave ether bond or a fluorine-containing alkylene group which has 1 to 5carbon atoms and may have ether bond; Rf⁵ is a fluorine-containing alkylgroup which has 1 to 10 carbon atoms and may have ether bond; Rf⁶ ishydrogen atom, an alkyl group having 1 to 10 carbon atoms or afluorine-containing alkyl group which has 1 to 10 carbon atoms and mayhave ether bond; n12 is 0 or
 1. 4. The fluorine-containing unsaturatedcyclic compound of claim 3, wherein Z³ is represented by the formula:

wherein Rf⁵ and Rf⁶ are as defined in said formula; n13 is 0 or aninteger of from 1 to 5; n14 is 0 or
 1. 5. The fluorine-containingunsaturated cyclic compound of claim 3, wherein Rf⁵ and Rf⁶ are the sameor different and each is a perfluoroalkyl group having 1 to 5 carbonatoms.